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Mono‐ and Dinuclear Carbonyl Complexes of (1,4,7‐Trimethyl‐1,4,7‐triazacyclononane)rhodium(I): Facile Migration of a C(O)OMe Ligand at a Dinuclear Rh(μ‐CO) 2 Rh Core
Author(s) -
de Bruin Bas,
Donners Jack J. J. M.,
de Gelder René,
Smits Jan M. M.,
Gal Anton W.
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(199803)1998:3<401::aid-ejic401>3.0.co;2-c
Subject(s) - chemistry , rhodium , ligand (biochemistry) , medicinal chemistry , stereochemistry , core (optical fiber) , catalysis , organic chemistry , receptor , biochemistry , materials science , composite material
The reaction of 1,4,7‐trimethyl‐1,4,7‐triazacyclononane (Cn*) with [{(CO) 2 Rh(μ‐Cl)} 2 ] in methanol at 0°C, followed by the addition of NH 4 PF 6 , results in the formation of the mononuclear carbonyl complex [Cn*Rh(μ‐CO) 2 ]PF 6 ([ 1 ]PF 6 ), the dinuclear carbonyl complex [Cn*Rh(μ‐CO) 3 RhCn*](PF 6 ) 2 {[ 2 ](PF 6 ) 2 } and the dinuclear methoxycarbonyl complex [Cn*Rh(C(O)OMe)(μ‐CO) 2 RhCn*]PF 6 ([ 3 ]PF 6 ). The reaction of [ 2 ](PF 6 ) 2 with NaOMe results in formation of [ 3 ]PF 6 by the attack of the methoxide at a bridging carbonyl. Treatment of [ 3 ]PF 6 with NH 4 PF 6 regenerates [ 2 ](PF 6 ) 2 , thus showing that the methoxylation of [ 2 ](PF 6 ) 2 is reversible. The structures of [ 1 ]PF 6 , [ 2 ](PF 6 ) 2 and [ 3 ]PF 6 have been determined by single‐crystal X‐ray diffraction. For [ 3 ]PF 6 an unprecendented facile, reversible, migration of the C(O)OMe ligand between the two rhodium centres of the Rh(μ‐CO) 2 Rh core is observed.