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Synthesis and Reactivity of an Aminocarbene Osmium Complex Formed by Double C–H Activation of a NCH 3 Unit
Author(s) -
Richter Birgit,
Werner Helmut
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.200900759
Subject(s) - chemistry , osmium , reactivity (psychology) , medicinal chemistry , double bond , stereochemistry , ligand (biochemistry) , phenylacetylene , chelation , ruthenium , catalysis , polymer chemistry , organic chemistry , medicine , biochemistry , alternative medicine , receptor , pathology
The reaction of [OsCl 2 (PPh 3 ) 3 ] ( 1 ) with i Pr 2 PCH 2 CH 2 NMe 2 in 2‐propanol under reflux affords the Fischer‐type aminocarbene complex cis , cis ‐[OsCl 2 {κ 2 ( C , P )‐CHN(CH 3 )CH 2 CH 2 P i Pr 2 }{κ 2 ( P , N )‐ i Pr 2 PCH 2 CH 2 NMe 2 }] ( 2 ) by double C–H activation of one NCH 3 group. While treatment of 2 with phenylacetylene leads to the vinylidene complex cis , trans ‐[OsCl 2 (C=CHPh){κ 2 ( C , P )‐CHN(CH 3 )CH 2 CH 2 P i Pr 2 }{κ( P )‐ i Pr 2 PCH 2 CH 2 NMe 2 }] ( 3 ) by partial opening of the P , N ‐chelate bond, the reaction of 2 with CO and CN t Bu gives rise to ionic compounds of type [OsCl(L){κ 2 ( C , P )‐CHN(CH 3 )CH 2 CH 2 P i Pr 2 }{κ 2 ( P , N )‐ i Pr 2 PCH 2 CH 2 OMe}]Cl ( 4 : L = CO, 5 : L = CN t Bu) by substitution of one chloro ligand. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)