SYNTHESIS AND REACTIONS WITH ALKYNES OF COMPLEXES CONTAINING BOTH PHOSPHORUS AND SULFUR BRIDGING LIGANDS - CRYSTAL AND MOLECULAR-STRUCTURES OF [MN2(LAMBDA-PPH2)-(LAMBDA-SPH)(CO)8], [CO3(LAMBDA-3-S)(LAMBDA-PPH2)(CO)6(PPH3)] AND [CO3(LAMBDA-3-S)(LAMBDA-PPH2CHCPH)(CO)6(PPH3)]

The metal carbonyls [Mn2(CO)10] and [Co2(CO)8] react with the ligand PPh2(SPh) to give respectively the binuclear complex [Mn2(mu-PPh2)(mu-SPh)(CO)8] 2 and a combination of trinuclear complexes [Co3(mu3-S)(mu-PPh2)(CO)7] 3, [Co3(mu3-S)(mu-PPh2)(CO)6(PPh3)] 4 and [Co3(mu3-S)(mu-PPh2)(CO)5(PPh3)2] 5 in a yield ratio which depends on the reaction conditions. Complex 4 reacts thermally with PhC=CH which inserts regiospecifically into the phosphido-bridge to generate [Co3(mu3-S)(mu-PPh2CHCPh)(CO)6(PPh3)] 6. A similar regiospecific insertion of alkyne to give the complex [Fe2{mu-PPh2CHC(CH2OH)}(mu-SPh)(CO)6] 7 takes place when [Fe2(mu-PPh2)(mu-SPh)(CO)6] 1 is treated with HOCH2C=CH under photolytic conditions. In contrast neither thermal nor photolytic reactions of 2 with alkynes could be induced. The crystal structures of 2, 4 and 6 have been determined.