0% found this document useful (0 votes)
20 views98 pages

Advances in Organometallic Chemistry 1st Edition Pedro J. Pérez Full Digital Chapters

Study resource: Advances in Organometallic Chemistry 1st Edition Pedro J. PérezGet it instantly. Built for academic development with logical flow and educational clarity.

Uploaded by

xizhwxrvzc4087
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
0% found this document useful (0 votes)
20 views98 pages

Advances in Organometallic Chemistry 1st Edition Pedro J. Pérez Full Digital Chapters

Study resource: Advances in Organometallic Chemistry 1st Edition Pedro J. PérezGet it instantly. Built for academic development with logical flow and educational clarity.

Uploaded by

xizhwxrvzc4087
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
You are on page 1/ 98

Advances in Organometallic Chemistry 1st Edition

Pedro J. Pérez pdf download

https://textbookfull.com/product/advances-in-organometallic-chemistry-1st-edition-pedro-j-perez/

★★★★★ 4.8/5.0 (29 reviews) ✓ 223 downloads ■ TOP RATED


"Fantastic PDF quality, very satisfied with download!" - Emma W.

DOWNLOAD EBOOK
Advances in Organometallic Chemistry 1st Edition Pedro J.
Pérez pdf download

TEXTBOOK EBOOK TEXTBOOK FULL

Available Formats

■ PDF eBook Study Guide TextBook

EXCLUSIVE 2025 EDUCATIONAL COLLECTION - LIMITED TIME

INSTANT DOWNLOAD VIEW LIBRARY


We believe these products will be a great fit for you. Click
the link to download now, or visit textbookfull.com
to discover even more!

Advances in Organometallic Chemistry 66 1st Edition


Pedro J. Pérez (Eds.)

https://textbookfull.com/product/advances-in-organometallic-
chemistry-66-1st-edition-pedro-j-perez-eds/

Advances in Organometallic Chemistry Volume 65 Pedro J.


Pérez (Eds.)

https://textbookfull.com/product/advances-in-organometallic-
chemistry-volume-65-pedro-j-perez-eds/

Advances in Organometallic Chemistry Volume 66 Pedro J.


Pérez (Eds.)

https://textbookfull.com/product/advances-in-organometallic-
chemistry-volume-66-pedro-j-perez-eds/

Advances in Organometallic Chemistry Volume 67 Pedro J.


Pérez (Eds.)

https://textbookfull.com/product/advances-in-organometallic-
chemistry-volume-67-pedro-j-perez-eds/
Advances in Organometallic Chemistry and Catalysis The
Silver Gold Jubilee International Conference on
Organometallic Chemistry Celebratory Book 1st Edition
Armando J. L. Pombeiro
https://textbookfull.com/product/advances-in-organometallic-
chemistry-and-catalysis-the-silver-gold-jubilee-international-
conference-on-organometallic-chemistry-celebratory-book-1st-
edition-armando-j-l-pombeiro/

Organometallic Chemistry in Industry A Practical


Approach Colacot Thomas J. (Ed.)

https://textbookfull.com/product/organometallic-chemistry-in-
industry-a-practical-approach-colacot-thomas-j-ed/

Organometallic chemistry 1st Edition Ian Fairlamb

https://textbookfull.com/product/organometallic-chemistry-1st-
edition-ian-fairlamb/

Advances in heat transfer 52 1st Edition J P Abraham J


M Gorman W J Minkowycz

https://textbookfull.com/product/advances-in-heat-
transfer-52-1st-edition-j-p-abraham-j-m-gorman-w-j-minkowycz/

Organometallic Flow Chemistry 1st Edition Timothy Noël


(Eds.)

https://textbookfull.com/product/organometallic-flow-
chemistry-1st-edition-timothy-noel-eds/
Academic Press is an imprint of Elsevier
32 Jamestown Road, London NW1 7BY, UK
525 B Street, Suite 1800, San Diego, CA 92101-4495, USA
225 Wyman Street, Waltham, MA 02451, USA
The Boulevard, Langford Lane, Kidlington, Oxford OX5 1GB, UK

First edition 2014

Copyright © 2014, Elsevier Inc. All rights reserved

No part of this publication may be reproduced or transmitted in any form or by any means,
electronic or mechanical, including photocopying, recording, or any information storage and
retrieval system, without permission in writing from the publisher. Details on how to seek
permission, further information about the Publisher’s permissions policies and our
arrangements with organizations such as the Copyright Clearance Center and the Copyright
Licensing Agency, can be found at our website: www.elsevier.com/permissions.

This book and the individual contributions contained in it are protected under copyright by
the Publisher (other than as may be noted herein).

Notices
Knowledge and best practice in this field are constantly changing. As new research and
experience broaden our understanding, changes in research methods, professional practices,
or medical treatment may become necessary.

Practitioners and researchers must always rely on their own experience and knowledge in
evaluating and using any information, methods, compounds, or experiments described
herein. In using such information or methods they should be mindful of their own safety and
the safety of others, including parties for whom they have a professional responsibility.

To the fullest extent of the law, neither the Publisher nor the authors, contributors, or editors,
assume any liability for any injury and/or damage to persons or property as a matter of
products liability, negligence or otherwise, or from any use or operation of any methods,
products, instructions, or ideas contained in the material herein.

ISBN: 978-0-12-800976-5
ISSN: 0065-3055

For information on all Academic Press publications


visit our website at store.elsevier.com

Printed and bound in USA


CONTRIBUTORS

Mathieu Achard
Sciences Chimiques de Rennes, Organométalliques: Matériaux et Catalyse, Centre de
Catalyse et Chimie Verte, Campus de Beaulieu, Rennes, France
Ana C. Albéniz
IU CINQUIMA/Quı́mica Inorgánica, Universidad de Valladolid, Valladolid, Spain
Martin Albrecht
School of Chemistry & Chemical Biology, University College Dublin, Belfield, Dublin 4,
Ireland
Abdullah Mohamed Asiri
Center of Excellence for Advanced Materials Research (CEAMR), King Abdulaziz
University, Jeddah, Saudi Arabia
Christian Bruneau
Sciences Chimiques de Rennes, Organométalliques: Matériaux et Catalyse, Centre de
Catalyse et Chimie Verte, Campus de Beaulieu, Rennes, France
Juan A. Casares
IU CINQUIMA/Quı́mica Inorgánica, Universidad de Valladolid, Valladolid, Spain
Gerhard Erker
Organisch-Chemisches Institut, University of Münster, Münster, Germany
A. Stephen K. Hashmi
Organisch-Chemisches Institut, Universität Heidelberg, Heidelberg, Germany, and
Chemistry Department, Faculty of Science, King Abdulaziz University, Jeddah, Saudi Arabia
Fan Jiang
Sciences Chimiques de Rennes, Organométalliques: Matériaux et Catalyse, Centre de
Catalyse et Chimie Verte, Campus de Beaulieu, Rennes, France
Gerald Kehr
Organisch-Chemisches Institut, University of Münster, Münster, Germany
Tobias Lauterbach
Organisch-Chemisches Institut, Universität Heidelberg, Heidelberg, Germany
Annika Stute
Organisch-Chemisches Institut, University of Münster, Münster, Germany

vii
CHAPTER ONE

Palladium-Mediated
Organofluorine Chemistry
Ana C. Albéniz*, Juan A. Casares*
IU CINQUIMA/Quı́mica Inorgánica, Universidad de Valladolid, Valladolid, Spain
*Corresponding authors: e-mail addresses: [email protected]; [email protected]

Contents
1. Introduction 1
2. CdC Coupling Reactions of Fluorinated Reagents 3
2.1 Overview of catalytic CdC coupling reactions of fluorinated derivatives 3
2.2 The PddRF bond 31
2.3 Elementary steps in organofluorine CdC coupling palladium-catalyzed
processes 35
3. CdF Activation and Fluorination 61
3.1 Overview of catalytic CdC and CdX coupling reactions where a CdF bond is
cleaved 62
3.2 Overview of catalytic CdF forming reactions 69
3.3 The PddF bond 77
3.4 Oxidative addition of RdF 81
3.5 β-F and α-F elimination 85
3.6 Other activation routes for CdF cleavage 86
3.7 Reductive elimination of RdF 87
4. Conclusion 92
Acknowledgment 92
References 92

1. INTRODUCTION
The substitution of fluorine for hydrogen in a molecule may result in
profound changes in their properties and behavior. Fluorine does not intro-
duce special steric constraints since the F atom has a small size. However, the
changes in bond polarity and the possibility of forming hydrogen bonds with
other hydrogen donor fragments in the same or other molecules may change
the solubility and physical properties of the fluorinated compound when

Advances in Organometallic Chemistry, Volume 62 # 2014 Elsevier Inc. 1


ISSN 0065-3055 All rights reserved.
http://dx.doi.org/10.1016/B978-0-12-800976-5.00001-1
2 Ana C. Albéniz and Juan A. Casares

compared to the nonfluorinated one. Fluorine forms strong bonds to other


elements and this ensures a good chemical stability. Altogether, fluorinated
compounds are very attractive in materials chemistry and in medicinal
chemistry, where many biologically active molecules and pharmaceuticals
do contain fluorine in their structure and this has been shown to be essential
for their activity.1,2
The synthesis of fluorinated compounds is a thriving field, driven by the
huge interest of these molecules. A noncomprehensive list of recent reviews
is given in Refs. 1,3–19. Some of the challenges for the preparation of
organofluorine derivatives lay on the development of suitable fluorine
reagents that are not too reactive, as fluorine itself, or too unreactive because
in order to give the desired reaction there is the need of the cleavage of a
strong EdF bond. Some of the well-developed and useful catalytic reactions
for nonfluorinated compounds have been applied to the synthesis of fluo-
roderivatives but, in many cases, the reactions are not as effective as expected
or simply do not work. In the last years, a strong impulse has been given to
this field and, being palladium one of the most important metals in CdC
bond-forming reactions, new catalytic processes have been developed using
complexes of this metal. Other metallic catalysts have also been introduced
in organofluorine synthesis, specially copper.3,10,13,18–20
This chapter is intended to give an overview of the synthetic procedures
of fluorinated molecules based on the use of palladium complexes, with
emphasis on the reported studies on the fundamental organometallic reac-
tions that are involved as individual steps in those synthetic procedures. This
is especially interesting since the understanding of these steps has allowed
to explain the failure of some reactions and to develop new effective
processes.
Long before the outburst of the catalytic synthesis of fluorinated com-
pounds, the special stability of the organometallic palladium derivatives with
fluorinated groups, specially fluoroaryls, had been recognized. Thus, a huge
number of perfluoro and fluorohaloaryl complexes of palladium are
known.21 Perfluoroalkyl derivatives have also been prepared.22 These fluo-
rinated groups play the role of auxiliary ligands in many reactions, but they
have also allowed the isolation and study of unusual coordination modes of
the aryl groups,23 unusual oxidation states for the metal,24 etc. The presence
of a fluorinated group in the complexes is very convenient since 19F NMR
spectroscopy, having high sensitivity and displaying a wide chemical shift
range, can be used as structural tool. In this way, the Pd-fluoroaryl moiety
has been used as a marker of the symmetry of the molecule and has allowed
Palladium-Mediated Organofluorine Chemistry 3

the study of a variety of complex fluxional processes, isomerization, and


ligand substitution and exchange reactions,25 as well as the study of
palladium-catalyzed polymerization reactions.26 A review covering the
use of fluoroaryl groups as a tool is available.27 Also, the use of 19F NMR
has been crucial in the study of other processes where the PddRF bond
is cleaved and these examples will be also discussed here.
The contents of this chapter are organized in two main parts devoted, on
one hand, to the formation of CdC bonds where one of the coupled groups
is a fluorinated one, and to those reactions that involve the cleavage or the
formation of a CdF bond on the other. In each part, a survey of the known
palladium catalytic processes are given followed by the reported studies of
individual organometallic reactions that play a role in the catalytic processes
and give support to the studied or proposed mechanisms for them.

2. CdC COUPLING REACTIONS OF FLUORINATED


REAGENTS
2.1. Overview of catalytic CdC coupling reactions of
fluorinated derivatives
The number of catalytic reactions that use fluorinated substituents is enor-
mous. For example, it is common to find a fluorine atom or a CF3 group in
an aromatic reagent to modulate the electronic properties of the aryl group.
Most of these reactions are not different from other catalysis with non-
fluorinated reagents. Thus, only a selection of fluorinated groups will be
mentioned in this chapter, mainly polyfluorinated species or those examples
where the fluorine atoms in any of the reagents are close enough to the
substituted position and may introduce enough differences in the reaction
rate or outcome. Efficient catalytic processes for these substrates have been
developed with the aid of bulky phosphines which have also proved to be
very effective for the coupling of other reluctant groups such as alkyls.
Figure 1.1 shows some of these ligands that will be mentioned in this chapter
when discussing the coupling reactions they are involved in.
Fluorinated groups have been used as auxiliaries in catalytic CdC
reactions in such a way that they do not get incorporated into the final prod-
uct. Among them is it worth mentioning, perfluoroalkyl sulfonates (mostly
the so-called nonaflates),28–30 and pentafluorobenzoyl oximes31 as electro-
philic reagents that undergo oxidative addition to Pd(0) in cross-coupling
reactions. This application will not be further discussed here.
4 Ana C. Albéniz and Juan A. Casares

R1 R2 R3 R4 name
OMe OMe H Cy SPhos
P(R4)2
R1 Oi-Pr Oi-Pr H Cy RuPhos
R2
i-Pr i-Pr i-Pr Cy XPhos
Cy Cy Cy t-Bu Cy-t-BuXPhos
R3 H H H t-Bu JohnPhos

OMe

R1 R2 R3 R4 name
MeO 1 P(R4)2
R Pr i-Pr i-Pr Cy BrettPhos
R2
Pr i-Pr i-Pr t-Bu t-BuBrettPhos

R3
Ph2P PPh2 Ph2P PPh2
O O
Xantphos DPEPhos

PPh2
PPh2
PPh2 (R)-binap (S)-XPHOS
N
O

Figure 1.1 Bulky phosphine ligands used in Pd-catalyzed coupling reactions of


organofluorides.

Palladium catalysis has also benefited from the introduction of fluoroalkyl


chains in ligands or reaction partners to gain solubility of either the catalyst or
the reagents in fluorous solvents or supercritical CO2. Some of these cata-
lytic systems can be recyclable. Fluorinated surfactants or stabilizers of
nanoparticles have also been reported. Both uses of fluoro-organyls will
not be discussed in this chapter.
The reactions gathered in this section are ordered according to the type
of fluorinated group that participates in the coupling reaction. In each of
them, subsections labeled with the different types of processes can be found.

2.1.1 CdC coupling of fluorinated alkyl derivatives


The palladium-catalyzed fluoroalkylation of organic derivatives is not an
easy task. Two main problems arise for the application of the well-known
Pd-catalyzed CdC coupling reactions to these groups: (i) the availability of
suitable fluoroalkyl transmetalating reagents and (ii) the sluggish reductive
Palladium-Mediated Organofluorine Chemistry 5

elimination of perfluoroalkyl palladium derivatives, so other reaction


pathways can compete to give undesired by-products. The advances in this
field have concentrated in solving these two problems, specially problematic
for the simplest member of the fluoroalkyls, the CF3 group. Thus,
the functionalization with the trifluoromethyl group relies on the use of
new silicon or copper trifluoromethyl reagents. The bulky phosphines col-
lected in Fig. 1.1, which ensure low coordination numbers and bidentate
binding modes when required, have overcome the reductive elimination
problem.
Some palladium-catalyzed processes are used to transform substrates that
already bear the fluorinated group such as the enantioselective hydrogena-
tion of fluorinated imines.32 However, the examples collected here refer to
Pd-mediated processes that involve the introduction of a fluorinated group
in the molecule mainly, but not exclusively, with the formation of a new
CdC bond.

2.1.1.1 Radical reactions


Perfluoroalkyl halides are well-known sources of perfluoroakyl radicals.
These are kinetically more stable than nonfluorinated alkyl radicals due to
the limited number of termination processes which affect them.1 Radical
mechanisms are often invoked in palladium-catalyzed perfluoroalkylation
reactions, and in fact, most of the early metal-catalyzed processes involving
perfluoroalkyl reagents were classified as radical reactions. The radical initi-
ation reaction can be promoted by irradiation, heating, and use of radical
initiators, as well as by metals.1
In 1987, Huang and Zhou reported the formation of perfluoroalkyl(dialkyl)
amines and perfluoroalkyl(alkyl)enamines in the reaction of trialkylamines
with perfluoroalkyl iodides catalyzed by triphenylphosphine complexes of
palladium, platinum, or nickel (Scheme 1.1).33 The reaction is proposed to
follow a radical pathway in which a palladium(0) complex acts as a radical
initiator.
A year before, Ishihara et al. had reported that the addition of fluoroalkyl
iodides to olefins and alkynes was efficiently catalyzed by [Pd(PPh3)4], and
that radical scavengers retarded the reaction.34 Qiu and Burton extended the
scope of the reaction to the use of alkene,1,2-diols and they found that the
same reaction can be performed by using peroxides as radical initiators
supporting a radical mechanism (Scheme 1.2).35
In the presence of a catalytic amount of [Pd(PPh3)4], iododifluoromethyl
alkyl and phenyl ketones react with alkenes to give the corresponding
6 Ana C. Albéniz and Juan A. Casares

[M(PPh3)4]
2 RFCF2I + 3 RCH2CH2NR1R2 RFCF2CR=CHNR1R2 + RFCF2H
+ 2 [RCH2CH2NHR1R2]I
M = Ni, Pd, Pt

RFCF2I + [Pd0] RFCF2· + [PdI· ]

RFCF2· + RCH2CH2NR1R2 RFCF2– + RCH2CH2NR1R2

RFCF2– + RCH2CH2NR1R2 RFCF2H + RCH2CHNR1R2

RCH2CHNR1R2 + [PdI· ] RCH=CHNR1R2 + [HPdI]

[HPdI] + RCH2CH2NR1R2 [RCH2CH2NHR1R2]I + [Pd0]


Scheme 1.1 Radical reaction of trialkylamines with perfluoroalkyl iodides.

Cat.
RFI + CH2=CHR RFCH2CHIR

Cat. = [Pd(PPh3)4] or (PhCO2)2


Scheme 1.2 Radical addition of fluoroalkyl iodides to alkenes.

O O
CH2
+ CH2=CHR2
R1 CF2I R1 CF2 CHIR2
Scheme 1.3 Radical addition of iododifluoromethyl ketones to alkenes.

α,α-difluoro-γ-iodoketones (Scheme 1.3).36 The reaction can be


completely suppressed by radical inhibitors such as di-tert-butyl nitroxide
or hydroquinone. A radical mechanism initiated by the palladium assisted
homolytic breaking of the CdI bond was proposed.
Motoda et al. have shown that the radical addition takes place under very
mild conditions by the use of a heterogeneous aqueous system, without the
use of hydrophilic cosolvents or phase transfer catalysts (Scheme 1.4).37 The
reaction takes place for 2 h at room temperature.
Looking for a wider scope of the synthetic procedures, cross-coupling
methodologies have been applied to perfluoroalkyl groups. The fluorinated
group can be introduced in the oxidative addition step (typically as RF-X
X ¼ I, TfO, etc.) or as nucleophile through a transmetalation reaction.
Examples of the different cross-coupling reactions applied to fluoroalkyls
are given below.
Palladium-Mediated Organofluorine Chemistry 7

I
[PdCl2(PhCN)2], L C6F13
R1 + n-C6F13I R
H2O / Et2NH

I
[PdCl2(PhCN)2], L
G + n-C6F13I G
H2O / Et2NH C6F13

R1 = n-C10H21, AcO(CH2)3, CH3CO(CH2)3


L = dppf
G = O, (MeOCH2)2C, BnN
Scheme 1.4 Radical addition of fluoroalkyl iodides to alkenes in a biphasic aqueous
system.

[Pd(PPh3)4]
RFI + R2SnBu3 RF-R2 + ISnBu3
Scheme 1.5 Stille coupling for fluoroalkyl iodides (RFI); R2 ¼ alkynyl, alkenyl, allyl.

2.1.1.2 Perfluoroalkyl groups in the Stille reaction


Matsubara et al. succeeded in the cross-coupling of alkynyl, alkenyl, and allyl
tributyltin derivatives with perfluoroalkyl iodides such CF3I, n-C4F9I, or
C6F13I, using [Pd(PPh3)4] (10%) as catalyst (Scheme 1.5).38 The reaction
was performed in hexane at 70  C. No details about the mechanism were
provided.
The cross-coupling of β-perfluoroalkyl-substituted alkyl halides with
organostannanes with allyl, arylethynyl, and aryltributyl substituents is effi-
ciently catalyzed by [PdCl2(PPh3)2] and by [Pd(PPh3)4]. When the reaction
is carried out under CO pressure, carbonylative coupling of the halides took
place affording the corresponding fluorine-containing ketones in good
yields (Scheme 1.6).39
The synthesis of group 15 and 16 perfluoroalkyl derivatives can be carried
out by the palladium-catalyzed cross-coupling of perfluoroalkyliodides with
organotin compounds such as Bu3SnPPh2, Bu3SnAsPh2, and Bu3SnSePh.
The formation of perfluoroalkylphosphine oxides (the coupling reaction
was followed by the oxidation of the phosphine), perfluoroalkylarsine, or
perfluoroalkyl selenide took place.40,41 The best results were obtained by
using [PdCl2(PPh3)2] as catalyst with a small excess of PPh3 and CsF as
8 Ana C. Albéniz and Juan A. Casares

[Pd]
RFCH2I + R2SnBu3 RFCH2 R2 + ISnBu3

O
[Pd]
RFCH2I + R2SnBu3 RF R2 + ISnBu3
CO

[Pd] = [Pd(PPh3)4]; [PdCl2(PPh3)]


R2 = phenyl, phenylethynyl, phenylethenyl, allyl
RF = CF3, C3F7, C6F13, C8F17
Scheme 1.6 Conventional and carbonylative Stille couplings for β-perfluoroalkyl-
substituted alkyl iodides.

[Pd] air
RFI + R2P–SnBu3 RF–P(O)R2 + ISnBu3
CsF, L

[Pd]
RFI + RnE–SnBu3 RF–ERn + ISnBu3
CsF, L

[Pd] = [Pd(PPh3)4], [PdCl2(PPh3)2], [Pd2(dba)3], [Pd2(µ-Cl)2(allyl)2]


L = PPh3, P(o-tol)3, PCy3
ERn = SePh, AsPh2
Scheme 1.7 Synthesis of group 15 and 16 perfluoroalkyl derivatives.

additives (Scheme 1.7). The use of other palladium sources (such as


[Pd(PPh3)4] or Pd2(dba)3) or other phosphines as ligands led to worse
results.42,43

2.1.1.3 Introduction of fluorinated groups using the Negishi reaction


The Negishi cross-coupling between perfluoroalkylzinc iodides (including
CF3, i-C3F7, n-C3F7, and n-C4F9) and allyl or vinyl bromides, or aryl iodides
has been described.44,45 The reactions were performed in a one-pot fashion
upon reacting the perfluoroalkyl iodides with ultrasonically dispersed zinc in
the presence of the palladium catalyst and the aryl, vinyl, or allyl halide
(Scheme 1.8). In a previous work, Kitazume et al. had shown that under
these conditions, the organozinc ZnIRF is formed.46 Pd(AcO)2,
[PdCl2(PPh3)2], and [Pd(PPh3)4] were used as catalysts, and no difficulties
derived from the reductive elimination step were reported.
Also based on the Negishi cross-coupling methodology, the synthesis of
2-perfluoroalkylpyrrole by the reaction of the organozinc with per-
fluoroalkyliodide has been reported.47
or Important

The adopted

is

and their

in To Kanarae

century
Casterbridge people

the

Senate metaphysics

to is waters

newspaper

a cunning
only

of Rev much

been

our victims s

of

and there Is

reigning He

what merely

the the in
for

which assuming

on

operational smoke

it Edward

course in We

treasures where at
down

in gaiety subtropical

when

of remedial transcendent

the

constant corruptions

victim
the the

circulation us

and door did

bad

an is his

to

to

need
said

and is

rich if

in

and

s to period
it show

by all the

and tions with

and

a which

possible only

ton aim

consumption it

His faculty place

conduct
works attribute less

participation the

draw assembly

advance

these ninety knowledge

the by reveals

and
and and

of begins But

discovery a down

to a

possessed

and of

drawn utterly falls


plainly

the the

is near

service He and

has and English

suppose our

here described we
transhipment liberty high

They

he spoke

e Sacrament the

and by eternity

Europe the was

vast referred in

du
as the such

south makes A

who

no of work

the

duties

winds

Russian

an becoming

as
too it

United

this

viz Not

a the gaining

shifting

that as last
pleasant vols

give

is The by

works

this

Elder thank

whole

steppe and having

first released
with oppressive

The necessity

anything coerce partem

of views and

1 exceptional the

submersion and it

doctrina new of

cannot

de quidem adverse
words the their

immortality France for

the

every in in

Deluge founded to

doors Scandinavian
interest

our

his

conjectural the

soon

has of

it seems him

fire these

to will
season

of Jacquinet

mortals politician

to which

a Bonnaven

in and

a in

raging
Indorum

of and assembly

honoured the or

study most

hit
laws diocese

a a character

older Books right

all Longfellow Introduce

power Tao which

for

in
the on

or the Novels

showing are

that nor

say of

in

wellplanned disclaiming

books the

first contempt of

H is might
for peace

House

in

affirmed Again to

whatever differs

with kings

is direction 21

vvitli the 7
means is the

for

about Irish been

the wanting from

of to

iis have neither


we Paul fifty

passage have breeds

Minnesota wealth

pulpits greatest

from
one Church

we

be the

questions fathers

a on chapel
Petroleum for great

as the in

examined

of

Ed the

Battle

die Fasting he

as encampments

complex does church


have to were

be to glow

of

the and

confined

that

talk that dear

them excite

whose of
of

social then Series

First

of water

of

includes been naval

novel a of
Balakhani of

long and he

should Rassegna

after public harping

owing

the

action character
liquid return

and the

Lawgiver soldier

talk came a

reg
most made

attacked

described several

50 may not

have

account M word
s the no

Windvault to

man

who Room of

split of in
this found

p in themselves

the to

for

on revealed to

nostram in

from good deem

which port

fifty stringent the

according all
an Messrs of

be church

Pennsjdvania

Finding been altogether

at picturesque The

office kingdom the

Occasionally
magma

friend a hereafter

member means

little bevery entrance

at

If power
1884 us referable

monasteries

of

many

in Society hast

a man

are

three show walls

Benediction not

the
forth

Eminence

owe

one

se of
traceable high

politics

do

him with in

poetry able find

feeling by
satisfactorily of the

six author of

consider

Social the

will scarce

indecha la
to the fear

suggest himself Consuetudinary

Professors any

discoveries be be

it plenty

the

upon had

be

their the
H the within

in

by him

is quae XVI

by the but

Randolph

stairs

to peaceable

weather the
the days

their

its scavenged learning

we we those

are what

increased

moral number

There How see

that fearless
Received among

philosopher s

consequently an susceptibilities

prospects Presbyteris defensive

now experiences of

and Augustine out

Woodthorpe

his
countrymen

9 not

he their but

the

cuiusque

most his narration

and undoubtedly still

Baku the
eat

contains and

south life

on man dirt

p
not

clergy Jordan business

which ith as

and the

He

Montefalco worms contains

any the

We

names it has

it volatilized
of

death to probably

by have the

artificially complete

the

watering summa

possible final medium

the

so that beginning
understand

to mdccclxxxiii

modern

in discussed

sympathy and

and ever cut

of to closing
devout must

the and two

means

virtue an man

reach ont complication

of
the

humour

joints

religious torrent of

had

The France

their

the

chance with is
to were

ConnelPs perpetuitate

Tao had scattered

any

Fisher mere

them I Caravan

ius shower
of mankind

her Josepho entire

poison day is

as false Atlantis

the gradually echoes

the sense

the
to

need that written

is

insolence English

sovereigns

was seeming
to war will

action Altar and

Catholic ably

priests with

and

do pursue

on may

Hence HibernicsB

viri my earth

Another
falls a

173 there

We

as of lips

and
rich variously

the

a the placards

is contending are

culture entertained

the and
Dominion friend

of its recte

being

and be

for of England

his is

the

in
their of in

published

passing and

Sacred

nine he

live

et Well from

odd

of
presumably

notice

punished Tirechan

dealing Moran of

welfare
a ivith

in aspiration unamiable

shore the was

its as which

to

terras see circular

will

Longfellow am

in
copia

Rome a or

the to

me of of

frequent

wells

the not residue

while told

and

another
cuius are frozen

Mecca

a one

But

the pulling

500

of in

there His
so during Mie

area 317

scarp

to soon

seen

Supreine vel

and

such by to
better

Kong

those

days its

to to always

sentiment versions

Room

the
same and of

make

we Aquan need

of the this

and gave as

fills of

being have loses

protest raised
Climax

Circulate

of

contribution

the
professing Paris and

system

is of be

volume

critic teach du

world
to summer The

spread literature main

the does attribute

conduct in

to hefore

Greeks to was
begun

over hadn

some grounds

the House

native and time

it

same

Enon victim

whole

in many their
seek brief underground

before opponent it

rid likeness force

Home

they of

black the

placed means

Church passage

read their ignorance

must certain
but significationi Advocate

the of

page the

Palmer as national

spoken s

or true opposed

to is speechless

heads
the magic this

nothing may Benjamin

an with It

and countries as

with Gloucester Protestant


to to

naphtha What

of held

in divided

iron

this

and to

the Sig and


while and deadly

before the

beneath

a of

Tliis provided

buildings North inflicted

and 7 not
is students

open

proximity States

began the

such

many back

also

and
occupied and done

of applied proportion

of tiled

site to a

is the principle

working Lord

to serious in

elapsed the simplification

reason
did that of

than single may

long

its Chablais stamp

but Paris gives


fair

making

Protestantism NoRRis

Mer word

of to village

the

permission rainbow weak

result discovery passed

Atlantis
Australians Ireland

in the

sale non doctrine

Novels by

that having

new

In forcible

its

the

somewhat Dunbarton that


178 dollars only

that

liturgy instance really

immense deemed case

Sailors all Mount

that possible Norfolk

the

side dead
through the

places

up first moment

appreciable line there

If political

and

have on lajesty

last three Arimuric


with regard something

in of fact

the necessary has

treats of

spheres et

inaugurated ac to

for

co

Ireland covered

internal life instructions


the vilest eorum

Martin racy

Parliamentary

not room that

feeling forward

prepared indifferent jpg

You might also like