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Reactivity of the Heavier Group‐13 Monochlorides [{CH(SiMe 3 ) 2 } 2 AlCl], InCl, TlCl, and of the Elements Ga and Hg Towards the Unsupported Ni‐Ni Bond of [{(η 5 ‐Cp)Ni(PEt 3 )} 2 ] — A Straightforward Synthetic Approach to the Synthesis of Mixed Main‐Group/Transition‐Metal Clusters Containing Unsupported Metal‐Metal Bonds
Author(s) -
Schneider Jörg J.,
Denninger Uwe,
Hagen Jörg,
Krüger Carl,
Bläser Dieter,
Boese Roland
Publication year - 1997
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.19971301013
Subject(s) - chemistry , disproportionation , metal , halogen , ligand (biochemistry) , crystallography , medicinal chemistry , stereochemistry , reactivity (psychology) , alkyl , organic chemistry , medicine , biochemistry , receptor , alternative medicine , pathology , catalysis
The dinuclear compound [{(η 5 —Cp)Ni(PEt 3 )} 2 ] ( 1 ) containing an unbridged Ni‐Ni bond reacts with the heavier group 13 monochlorides [{CH(SiMe 3 ) 2 ) 2 }Al III Cl], InCl, and TlCl by scission of the metal‐metal bond. In the case of InCl and TlCl the chloro‐bridged dimmers [{(η 5 ‐Cp)Ni(PEt 3 ) 2 ECl 2 Ecl} 2 ] (E = In 2 , Tl 5 ) were formed. The Tl compound 5 is unstable and decomposes via disproportionation a and formation of the halogen‐free Tl [III] compound [{(η 5 ‐Cp)Ni(PEt 3 )} 3 Tl] ( 6 ). 2 can be dehalogenated with activated magnesium to yield the halogen‐free In [III] compund [{(η 5 ‐Cp}Ni(PEt 3 )} 3 In] ( 4 ). The Ga analogue of 4 and 6 [{(η 5 ‐Cp)Ni(PEt 3 )} 3 Ga] ( 7 ) is accessible by a conproportionation of 1 with Ga metal in refluxing THF. In contrast to InCl and TlCl the aluminium (III) monochloride [{CH(SiMe 3 ) 2 } 2 AlCl] reacts with 1 by a ligand redistribution reaction and formation of the salt [{(η 5 ‐Cp)Ni(PEt 3 ) 2 ] + ‐[{CH(SiMe 3 ) 2 ] 2 AlCl] 2 − . ( 8 ). Elemental Hg or Mg amalgam show the same activity as elemental Ga towards 1 and insert into the NiNi bond by forming the linear Hg‐bridged complex [(n 3 ‐Cp)Ni(PEt 3 )] 2 Hg] ( 9 ). The molecular structures of 2, 4, 8 , and 9 were determined by X‐ray crystallography. The In atom in 4 has a distorted trigonal‐planar configuration with the central In atom being surrounded by three [(n 5 ‐Cp)Ni(PEt 3 )] fragments. 4 represents the first Ni‐In cluster containing exclusively unsupported In—Ni bonds, as well as the first carbonyl‐free Ni—In cluster. On the basis of spectroscopic data the same structure is assigned to the Ga and Tl analogues of 4 . The NiHgNi arrangement in 9 is exactly linear, as determined by X‐ray crystallography.