652969-70-5Relevant articles and documents
Enhanced C-C bond formation of heterodinuclear methylplatinum-molybdenum complexes having a hemilabile ligand with dialkyl acetylenedicarboxylate
Tsutsuminai, Susumu,Komine, Nobuyuki,Hirano, Masafumi,Komiya, Sanshiro
, p. 44 - 53 (2004)
Heterodinuclear methylplatinum-molybdenum complexes having a hemilabile P-L ligand, (P-L)MePt-MoCp(CO)3 (P-L = Ph2PC2H4NEt2 (1), Ph2PC2H4CH=CH2 (2)), react with dialkyl acetylenedicarboxylate to afford the novel heterodinuclear complexes (P-L)MePt-{μ-η2:η2-C(O)C2 (CO2R)2}MoCp(μ-CO)(CO) (P-L = Ph2PC2H4NEt2, R = Me (5); P-L = Ph2-PC2H4CH=CH2, R = Me (6); P-L = Ph2PC2H4NEt2, R = Et (7)). An X-ray diffraction study of 5 has revealed that the complex has a unique structure containing a platinacyclobutenone framework, where the φ-bond coordinates to the molybdenum. Heating of 5 at 50°C for 2 days results in reductive elimination of methyl and alkenyl ligands followed by decarbonylation to form the new μ-alkenyl type complexes (Ph2PC2H4NEt2-κ2N,P ) {μ-MeO2C(Me)=CCO2-Me}Pt-MoCp(μ-CO)(CO) (8) and (Ph2PC2H4NEt2-κ1P) (CO){μ-MeO2C(Me)=CCO2Me}Pt-MoCp (μ-CO)(CO) (9). Reactions of 5 with tBuNC or PMe3 cause selective ligand displacement of the amino moiety in the P-N ligand to form (Ph2PC2H4NEt2-κ1P) (L′)MePt {μ-η2:η2-C(O)C2(CO2 Me)2}MoCp(μ-CO)(CO) (L′ = tBuNC (10), PMe3 (11)). On the other hand, nucleophiles such as H2NBu, HNEt2, pyrrolidine, and KOPh add to acyl carbon to give the trisubstituted μ-alkenyl type complexes (Ph2PC2H4NEt2-κ2N,P )Me {μ-MeO2C(R2NCO)C=CCO2Me}Pt-MoCp(μ-CO)(CO) (NR2 = NHBu (12), NEt2 (13), NC4H8 (14)) and K+[(Ph2PC2H4- NEt2-κ1O)Me{μ-MeO2C(PhO2C)C =CCO2Me}Pt-MoCp(μ-CO)(CO)]- (15).
