Coordination complexes of acetylenic phosphines and diphosphines : V. Acetylene bridged derivatives of dicobalt octacarbonyl |
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Authors: | HA Patel AJ Carty NK Hota |
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Institution: | Department of Chemistry, University of Waterloo, Waterloo, Ontario Canada |
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Abstract: | Reactions of the phosphinoacetylenes RR′PCCR″ (R R′ Ph, R″ H, CF3, Ph, Me, t-Bu; R R′ C6F5, R″ Ph, Me; R Ph, R′ Me, R″ Me) with Co2(CO)8 have been studied. Complexes of four types have been characterised: (A)(RR′PC2R″)CO2(CO)6 (R R′ C6F5, R″ Ph, Me; R R′ Ph, R″ t-Bu), (B) (RR′PC2R″)2Co4(CO)10 (R R′ Ph, R″ H, CF3, Ph, Me; R R′ C6F5, R″ Me; R Ph, R′ Me, R″ Me), (C) (RR′PC2R″)2Co2(CO)6 (R R′ Ph, R″ t-Bu), (D) (RR′P(O)C2R″)Co2(CO)6 (R R′ Ph, R″ t-Bu; R R′ C6F5, R Ph). The complexes were characterised by microanalysis, IR, NMR and where possible mass spectra. Substitution reactions of the complexes with tertiary phosphites are described. In complexes of type (A) only the alkyne function is utilised whereas the tetranuclear compounds (B) have structures in which both alkyne and phosphorus moieties are coordinated. Compounds of type (C) are simple disubstituted phosphine complexes of Co2(CO)8 and those of type (D) are μ-alkyne derivatives of acetylenic phosphine oxides. The mechanism of formation of complexes of type (B) is discussed in the light of IR data. |
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