磷硼加合物晶体结构研究：n-Pr3P·BBr3与I3P·BBr3

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该资源是一篇关于磷-硼加合物化学的学术论文，主要讨论了两种特定的磷-硼化合物n-Pr3P[BBr3]和I3P[BBr3]的晶体结构。这篇论文由Christoph Aubauer、Katherine Davidge、Thomas M. KlapoÈtke、Peter Mayer、Holger Piotrowski和Axel Schulz共同撰写，来自慕尼黑的Ludwig-Maximilians-UniversitaÈt化学系。文章于2000年6月7日接收。文章摘要指出，n-Pr3P[BBr3]（三棱柱状，空间群P 4c1，Z = 4，晶格参数a = 11.5423(6) Å，b = 11.5423(6) Å，c = 13.8066(7) Å）和I3P[BBr3]（正交，空间群Pnma，Z = 4，a = 12.761(2) Å，b = 11.427(1) Å，c = 7.3728(7) Å）的结构通过X射线晶体学方法确定。研究发现，I3P[BBr3]中的P-B距离为2.01(1) Å，显著长于n-Pr3P[BBr3]中的1.95(1) Å。这表明不同类型的磷卤化物（如PX3，X = Cl, Br, I）和烷基磷的 Lewis 基性存在差异。论文通过自然键轨道（NBO）分析探讨了电荷转移和这些供体-受体复合物的键况。同时，利用拉曼光谱和红外光谱对n-Pr3P[BBr3]的部分频率进行了归属，并与I3P[BBr3]的正常模式进行了比较。关键词涵盖了晶体结构、NBO分析和Lewis基础性等主题，反映了研究的核心内容。论文深入研究了磷-硼加合物的结构特性，这对于理解这些化合物的化学行为和可能的应用具有重要意义，特别是在有机合成、材料科学以及化学键理论等领域。

Crystal Structures of the Phosphorus-Boron Adducts n-Pr

P ´ BBr

and I

P ´ BBr

Christoph Aubauer, Katherine Davidge

, Thomas M. Klapo

tke*, Peter Mayer, Holger Piotrowski,

and Axel Schulz

Munich, Ludwig-Maximilians-UniversitaÈt, Department of Chemistry

Received June 7

2000.

Abstract. The structures of the phosphorus-boron adducts n-

P ´ BBr

(trigonal, space group P 4 c1, Z =4,

a = 11.5423(6), b = 11.5423(6) and c = 13.8066(7) A

) and

P ´ BBr

(orthorhombic, space group Pnma, Z =4,

a = 12.761(2), b = 11.427(1), c = 7.3728(7) A

) were deter-

mined by X-ray crystallography. The P±B distance of

2.01(1) A

in I

P ´ BBr

is significantly longer than the P±B

bond in n-Pr

P ´ BBr

(1.95(1) A

). The different Lewis basi-

city of phosphorus halides, PX

(X = Cl, Br, I), and alkylpho-

sphines is discussed. The charge transfer and the bond situa-

tion in these donor-acceptor complexes is studied on the

basis of NBO analysis. Selected frequencies of n-Pr

P ´ BBr

obtained by Raman and infrared spectroscopy are assigned

and compared with the normal modes of I

P ´ BBr

Keywords: Crystal structure; NBO analysis; Lewis basicity;

Phosphorus boron halide complexes; Vibrational spectro-

scopy

Kristallstrukturen der Phosphor-Bor Addukte n-Pr

P ´ BBr

und I

P ´ BBr

Inhaltsu

bersicht. Die Strukturen der Phosphor-Bor-Addukte

n-Pr

P ´ BBr

(trigonal, Raumgruppe P 3 c1, Z =4,

a = 11.5423(6), b = 11.5423(6) and c = 13.8066(7) A

) und

P ´ BBr

(orthorhombisch, Raumgruppe Pnma, Z =4,

a = 12.761(2), b = 11.427(1), c = 7.3728(7) A

) wurden durch

RoÈntgenstrukturanalyse aufgeklaÈrt. Der P±B-Abstand in

P ´ BBr

ist mit 2.01(1) A

bedeutend laÈnger als in

n-Pr

P ´ BBr

(1.95(1) A

). Die unterschiedliche Lewis-Basizi-

taÈt von Phosphorhalogeniden, PX

(X = Cl, Br, I), und Al-

kylphosphinen wird diskutiert. Der Ladungstransfer und die

chemische Bindung in diesen Donor-Akzeptor-Komplexen

werden auf der Basis von NBO-Analysen erklaÈrt. Raman-

und Infrarot-Spektren von n-Pr

P ´ BBr

werden mit den

Normalschwingungen von I

P ´ BBr

verglichen.

Introduction

Boron trihalides are widely used in chemical synthesis

as Lewis acids and alkyl phosphines as Lewis bases.

Both species are of great importance in modern chem-

istry [1]. The central boron atom has only six valence

electrons and therefore, it represents an electron defi-

cient species which shows a strong affinity for electron

density especially from lone pairs of a donor molecule.

(X = Cl, Br, I) molecules represent only weak do-

nor molecules whereas alkyl phosphines form stronger

Lewis acid-base complexes. Although Lewis acid-base

complexes of phospines with boron halides have been

known for over four decades, only a few X-ray data of

these species are available [2±5].

Recently, we have been interested in the calculation

of Raman and IR spectra of phosphorus halide com-

pounds and phosphorus boron halide adducts. Vibra-

tional assignments of the normal modes for these Le-

wis acid-base adducts have been made on the basis of

comparison between theoretically obtained and ex-

perimentally observed Raman and IR data. Moreover

we have investigated the bonding and electron trans-

fer within these species [6±8].

Previous work has shown that the donor behavior

of phosphorus trihalides depends on the electronega-

tivity of the halogen substituents [9, 10]. For the phos-

phorus trihalides, the order of stability for the 1 : 1 do-

nor-acceptor complexes with boron trihalides is

PCl

< PBr

< PI

[11].

In this paper we want to report on the structural

and electronic properties of n-Pr

P ´ BBr

and

P ´ Br

Results and Discussion

The Lewis acid-base adduct n-Pr

P ´ BBr

(1) was pre-

pared from the reaction of tri-n-propylphosphine with

boron tribromide in pentane in a 1 : 1 molar ratio

under nitrogen and recrystallized from toluene.

P ´ BBr

(2) was prepared according to the literature

[2]. Crystals of 2 were obtained by recrystallization

from CS

Z. Anorg. Allg. Chem. 2000, 626, 2373±2378 Ó WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2000 0044±2313/00/6262373±2378 $ 17.50+.50/0 2373

present address: Department of Chemistry, University of

Glasgow, Glasgow G12 8QQ, Scotland (U.K.)

* Prof. Dr. Thomas M. KlapoÈtke,

Department of Chemistry, Ludwig-Maximilians-UniversitaÈt,

Butenandtstr. 5±13 (Haus D), D-81377 Munich, Germany

e-mail:tmk@cup.uni-muenchen.de

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