Reactions of Ru-3(mu-H)(mu(3)-CCCPh2)(mu-OH)(CO)(9) (1) with alkynes and 1,3-diynes are described. With HCequivalent toCSiMe(3), sequential formation of Ru-3{mu(3)-CH(SiMe3)CHCC=CPh2}(mu-OH)(CO)(9) (3) and Ru-3{mu(3)-Me3SiCCHCHC(SiMe3)-CC=CPh2}(CO)(8) (4) occurred, whereas with HCequivalent toCPh, the two isomeric complexes Ru-3(mu(3)-CRCR'CR'CRCC=CPh2)-(CO)(8) [R = Ph, H, (5a), R' = H, Ph (5b)] were isolated. These are formed by insertion of the alkyne into an Ru-C bond, with migration of the cluster H atom to the organic ligand. For 5, elimination of the OH group with one alkyne H atom gives water. The metallabenzene complex Ru-3{mu(3)-(FcCCH)(2)CC=CPh2}(CO)(9) (6) was obtained from 1 and HC=CFc. The allenyl cluster Ru-3{mu(3)-Ph2CCC(CPh=CHPh)}(mu-OH)(CO)(9) (7) is formed from 1 and PhCequivalent toCPh. The allenyl complex Ru-3{mu(3)-Me3SiCC(Cequivalent toCSiMe(3))CC=CPh2}(mu-OH)(CO)(9) (8), formed from 1 and Me(3)SiCequivalent toCCequivalent toCSiMe(3), and with a structure analogous to that of 3, undergoes isomerisation on heating to yield Ru-3{mu(3)-Ph2CCCC(Cequivalent toCSiMe(3))=CHSiMe3}(mu-OH)(CO)(9) (9) by slippage of the organic ligand over the cluster. The reaction between 1 and FcCequivalent toCCequivalent toCFc affords Ru-3{mu(3)-Ph2CCCC(Cequivalent toCFc)=CHFc}(mu-OH)(CO)(9) (10), with a structure analogous to that of 9. [References: 35]
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