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Different Reactivity Patterns in Dinuclear Pyrazolate‐Bridged Complexes: Stereoselective Formation of Ketonic Carbonyls
Author(s) -
Carmona Daniel,
Ferrer Joaquina,
Arilla José Miguel,
Reyes Josefa,
Lahoz Fernando J.,
Elipe Sergio,
Modrego Javier,
Oro Luis A.
Publication year - 2000
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(200001)2000:1<159::aid-ejic159>3.0.co;2-6
Subject(s) - chemistry , medicinal chemistry , p cymene , metal , ligand (biochemistry) , reactivity (psychology) , stereochemistry , ketone , enantiomer , yield (engineering) , ruthenium , chloride , catalysis , organic chemistry , medicine , biochemistry , materials science , receptor , alternative medicine , pathology , metallurgy
The metal–metal bonded dicarbonyl compounds [(η 6 ‐ p ‐cymene)M(μ‐pz) 2 IrCl(CO) 2 ]( M–Ir ) react stereospecifically with PPh 3 to yield an enantiomeric pair of ketonic carbonyl compounds [(η 6 ‐ p ‐cymene)M(μ‐CO)(μ‐pz) 2 IrCl(CO)(PPh 3 )] [M = Ru ( 1 ), Os ( 2 )] in which the chloride ligand is trans to the bridging ketone group. However, the non metal–metal bonded isomers [(η 6 ‐ p ‐cymene)MCl(μ‐pz) 2 M′(CO) 2 ], under similar conditions, eliminate CO forming the monosubstitution products [(η 6 ‐ p ‐cymene)MCl(μ‐pz) 2 M′(CO)(PPh 3 )] [M = Ru; M′ = Ir ( 3 ), Rh ( 4 ). M = Os; M′ = Rh ( 5 )]. Removal of the chloride ligand in 1 affords [RuIr(η 6 ‐ p ‐cymene)(CO) 2 (PPh 3 )(pz) 2 ]BPh 4 as two isomers, 6a , b . The related OsIr compound [(η 6 ‐ p ‐cymene)Os(μ‐CO)(μ‐pz) 2 Ir(CO)(PPh 3 )]BPh 4 ( 9 ) has been prepared from [(η 6 ‐ p ‐cymene)Os(CO)(μ‐pz) 2 Ir(CO) 2 ]BPh 4 ( 7 ) and PPh 3 . Again, the OsRh tricarbonyl related to 7 [(η 6 ‐ p ‐cymene)Os(CO)(μ‐pz) 2 Rh(CO) 2 ]BPh 4 ( 8 ) reacts differently with PPh 3 affording [(η 6 ‐ p ‐cymene)Os(CO)(μ‐pz) 2 Rh(CO)(PPh 3 )]BPh 4 ( 10 ).