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Intramolecular Carbyne–Isocyanide Coupling to an Alkyne Ligand at a d 4 Tungsten Center
Author(s) -
Filippou Alexander C.,
Lungwitz Bernhard,
KociokKöhn Gabriele
Publication year - 1999
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(199911)1999:11<1905::aid-ejic1905>3.0.co;2-w
Subject(s) - chemistry , carbyne , decarbonylation , alkyne , isocyanide , carbene , ligand (biochemistry) , intramolecular force , stereochemistry , medicinal chemistry , photochemistry , organic chemistry , catalysis , biochemistry , receptor
Oxidative decarbonylation of Cp*(CO) 2 W≡CNEt 2 ( 1 ) with PhICl 2 affords the aminocarbyne complex cis ‐Cp*(Cl) 2 (CO)W≡CNEt 2 ( 2 ), which reacts with t BuNC to give the CO substitution product cis ‐Cp*(Cl) 2 ( t BuNC)W≡CNEt 2 ( 3 ) (Cp* = C 5 Me 5 ). Complex 3 undergoes a carbyne–isocyanide coupling reaction with HCl to yield the alkyne complex Cp*(Cl) 3 W[η 2 ‐ t Bu(H)NC≡CNEt 2 ] ( 4 ). In comparison, the reaction of cis ‐Cp*(Cl) 2 [P(OMe) 3 ]W≡CNEt 2 ( 5 ) with HCl affords the 16e carbene complex Cp*(Cl) 3 W=C(H)NEt 2 ( 6 ) after elimination of P(OMe) 3 . Complex 5 was obtained from the CO ligand‐exchange reaction of 2 with P(OMe) 3 . Treatment of 6 with t BuNC yields the cationic 18e carbene complex [Cp*(Cl) 2 ( t BuNC) 2 W=C(H)NEt 2 ]Cl ( 7 ). The mechanism of the C–C coupling reaction of 3 to give 4 is discussed and the crystal structures of 4 and 6 are described.