Premium
Reactivity of {Ru(C 5 Me 5 )[η 2 ‐ P , O ‐Ph 2 PCH 2 C( t Bu)=O](CO)}[PF 6 ] towards Terminal Alkynes and Unexpected Rearrangement of a Fischer‐Type Carbene Ligand
Author(s) -
Demerseman Bernard,
Toupet Loïc
Publication year - 2009
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.200900574
Subject(s) - chemistry , ruthenium , isomerization , reactivity (psychology) , carbene , medicinal chemistry , dichloromethane , ligand (biochemistry) , stereochemistry , crystal structure , ether , methanol , solvent , crystallography , catalysis , organic chemistry , medicine , biochemistry , alternative medicine , receptor , pathology
The ruthenium complex {Ru(C 5 Me 5 )[η 2 ‐ P , O ‐Ph 2 PCH 2 C( t Bu)=O](CO)}[PF 6 ] reacts with terminal alkynes HC≡CR (R = H, t Bu, Ph) in methanol to afford {Ru[ : C(OMe)CH 2 R](C 5 Me 5 )[η 1 ‐ P ‐Ph 2 PCH 2 C(=O) t Bu](CO)}[PF 6 ] derivatives. The similar reaction conducted in dichloromethane as solvent led to six‐membered metallacyclic complexes{Ru(C 5 Me 5 )[η 2 ‐ C,P ‐ : C(CH 2 R)OC( t Bu)=CH–PPh 2 ](CO)}[PF 6 ], which, when R is an aromatic group (R = Ph, p ‐tolyl), rearrange under moderate thermal activation into {Ru(C 5 Me 5 )[η 3 ‐ C , C , P ‐RCH=CH‐OC( t Bu)=CHPPh 2 ](CO)}[PF 6 ] derivatives, according to an isomerization of a Fischer‐type carbene ligand into an η 2 ‐coordinated vinylic ether, as shown by X‐ray single crystal analysis (R = p ‐tolyl).(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)