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Syntheses, Crystal Structures and Reactivity of Organometallic Tantalum( IV ) Phosphinidene Complexes: trans ‐[{Cp*TaCl(μ‐PR)} 2 ] (Cp* = C 5 Me 5 , R = Cy, t Bu, Ph), cis ‐ and trans ‐[{Cp*TaCl(μ‐PMes)} 2 ] (Mes = 2,4,6‐Me 3 C 6 H 2 ) and cis ‐[{Cp′TaCl(μ‐PMes)} 2 ] (Cp′ = C 5 H 4 Me)
Author(s) -
Blaurock Steffen,
HeyHawkins Evamarie
Publication year - 2002
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 - 10.1002/1099-0682(200211)2002:11<2975::aid-ejic2975>3.0.co;2-1
Subject(s) - chemistry , phosphinidene , crystal structure , reactivity (psychology) , benzophenone , stereochemistry , medicinal chemistry , acetonitrile , acetone , crystallography , photochemistry , organic chemistry , medicine , alternative medicine , pathology
The reaction of [Cp*TaCl 4 ] (Cp* = C 5 Me 5 ) with LiPHR (1:1 or 1:2) gives the phosphinidene‐bridged tantalum( IV ) complexes trans ‐[{Cp*TaCl(μ‐PR)} 2 ] [R = Cy ( 1 ), t Bu ( 2 ), Ph ( 3 ), 2,4,6‐Me 3 C 6 H 2 (Mes) ( 4b )]. When the reaction with LiPHMes is carried out in a 1:1 ratio, cis ‐[{Cp*TaCl(μ‐PMes)} 2 ] ( 4a ) is also formed besides 4b . For comparison, cis ‐[{Cp′TaCl(μ‐PMes)} 2 ] ( 5 ) was prepared from [Cp′TaCl 4 ] (Cp′ = C 5 MeH 4 ) and LiPHMes (1:1). 1−5 are diamagnetic and were characterised spectroscopically (IR, MS; 1 H, 31 P, 13 C NMR). Crystal structure determinations on 1−5 showed the presence of dimeric phosphinidene‐bridged Ta IV complexes. The phosphinidene‐bridged complexes 1 , 3 and 4b do not react with acetone, benzophenone, acetonitrile, CS 2 ( 1 , 3 ), acetaldehyde ( 4b ), or ethylaluminum dichloride ( 3 ). 3 reacts with moist acetone in the presence of traces of air to give the trinuclear cluster [{Cp*TaCl(μ 2 −O)} 3 (μ 3 ‐O)(μ 2 ‐O 2 PHPh)}] ( 6 ) in very low yield. With an excess of CyNC, 3 gives [Cp*TaCl(CNCy) 4 ]Cl ( 7 ), which was characterised by 1 H and 13 C NMR spectroscopy and by crystal structure determination. As a minor product, [(Cp*TaCl 2 ) 2 (μ 2 ‐O)(η 2 ,μ 2 ‐P 2 Cy 2 )] ( 8 ) was also obtained in the reaction of [Cp*TaCl 4 ] with LiPHCy. 6 and 8 were only characterised by crystal structure determination. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)