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Synthesis and Molecular Structure of Six‐Coordinate Dichlorodihydridoruthenium(IV) and Five‐Coordinate Vinylideneruthenium(II) Complexes
Author(s) -
Wolf Justin,
Stüer Wolfram,
Grünwald Claus,
Gevert Olaf,
Laubender Matthias,
Werner Helmut
Publication year - 1998
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/(sici)1099-0682(199811)1998:11<1827::aid-ejic1827>3.0.co;2-q
Subject(s) - chemistry , phenylacetylene , crystal structure , carbene , stereochemistry , ligand (biochemistry) , derivative (finance) , medicinal chemistry , crystallography , catalysis , organic chemistry , biochemistry , receptor , financial economics , economics
The dichlorodihydridoruthenium(IV) compound [RuH 2 Cl 2 (P i Pr 3 ) 2 ] ( 4 ) was prepared from [RuCl 2 (C 8 H 12 )] n ( 3 ), P i Pr 3 , and H 2 in 2‐butanol via the chlorohydridoruthenium(II) derivative [RuHCl(H 2 )(P i Pr 3 ) 2 ] ( 5 ) as an intermediate. The synthesis of 5 was achieved under similar conditions from 3 , P i Pr 3 , H 2 , and 2‐butanol in the presence of NEt 3 . Compound 4 , which was characterized by X‐ray crystal structure analysis, reacts with excess phenylacetylene to give the phenylvinylidene complex [RuCl 2 (=C=CHPh)(P i Pr 3 ) 2 ] ( 7 ) and with propargylic alcohols or derivatives thereof to afford the vinylcarbene complexes [RuCl 2 (=CHCH=CR 2 )(P i Pr 3 ) 2 ] ( 9 , 10 ), respectively. From 5 and terminal alkynes RC≡CH the chlorohydridovinylidene compounds [RuHCl(=C=CHR)(P i Pr 3 ) 2 ] ( 11 , 12 ) were obtained. The phenylvinylidene complex [RuCl 2 (=C=CHPh)(PCy 3 ) 2 ] ( 15 ) was prepared from phenylacetylene and either [RuH 2 Cl 2 (PCy 3 ) 2 ] ( 14 ) or one of the carbene deriva‐tives [RuCl 2 (=CHR)(PCy 3 ) 2 ] ( 16 , 17 ) as starting materials. The X‐ray crystal structure analysis of 15 confirms a distorted square‐pyramidal geometry with the vinylidene ligand in the apical position. The interconversion of 4 to 5 and of the tricyclohexylphosphane counterparts 14 to 13 was achieved by hydrogen transfer from 2‐propanol in the presence of PR 3 . The reverse reaction occurs upon treatment of 5 or 13 with the corresponding phosphonium salt [HPR 3 ]Cl or HCl, respectively.