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Synthesis and Characterisation of Ternary Cage Compounds with Adamantane‐Like M 4 P 4 Si 2 (M = Al, Ga, In) Core Structures
Author(s) -
von Hänisch Carsten
Publication year - 2003
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200300156
Subject(s) - chemistry , crystallography , triclinic crystal system , adamantane , ternary operation , nuclear magnetic resonance spectroscopy , lattice constant , metal , silicon , crystal structure , stereochemistry , diffraction , organic chemistry , physics , computer science , optics , programming language
The reactions of [LiAl(PH 2 ) 4 ] or [NaAl(PH 2 ) 4 ] with Et 2 SiCl 2 or i Pr 2 SiCl 2 yield the dialkyldiphosphanylsilanes Et 2 Si(PH 2 ) 2 ( 1 ) and i Pr 2 Si(PH 2 ) 2 ( 2 ), respectively. Both compounds were identified by NMR spectroscopy as well as mass spectrometry. Compound 2 reacts with MEt 3 (M = Al, Ga, In) to form the cage compounds [ i Pr 2 Si{P(H)MEt 2 } 2 ] 2 ( 3 : M = Al, 4 : M = Ga, 5 : M = In). These three clusters were fully characterised by NMR and IR spectroscopy as well as by single‐crystal X‐ray diffraction. The central structural motif of 3 − 5 is an adamantane‐like cage composed of four metal, four phosphorus and two silicon atoms. They are the first ternary clusters with these combinations of elements and crystallise isotypical in the triclinic space group P $\bar 1$ ; the lattice constants are: 3 : a = 1129.0(6), b = 1164.8(8), c = 1750.6(8) pm; α = 83.63(5), β = 81.53(4), γ = 73.39(5)°; 4 : a = 1125.9(7), b = 1159.0(7), c = 1744.7(7) pm; α = 83.71(4), β = 81.89(4), γ = 73.05(5)°; 5 : a = 1147.4(2), b = 1174.7(2), c = 1753.3(4) pm; α = 85.32(3), β = 82.03(3), γ = 73.40(3)°. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)