Treatment of [Ry(CH=CHCH2PPh3)X(CO)(PPh3)2]+ (X=Cl, Br) with KTp (Tp=hydridotris(pyrazolyl)borate) and NaBPh4 prouced [TpRu(CH=CHCH2PPh3)(CO)(PPh3)]BPh4. Reaction of RuHCl(CO)(PPh3)3 with HC=CCH(Oet)2 produced Ru (CH=CHCH(Oet)2)Cl(CO)(PPh3)2, which rected with KTp to give TpRu(CH=CHCHO)(CO)(PPh3). Treatment of [TpRu(CH=CHCH2PPh3)(CO)(PPh3)]BPh4 with NaN(SiMe3)2 and benzaldehyde produced TpRu(CH=CHCH=CHPh)(CO)(PPh3). The later complex was also produced when TpRu(CH=CHCHO)(CO)(PPh3) was treated with PhCH2PPh3Cl/NaN(SiMe3)2. The bimetallic complex [TpRu(CO)(PPh3)]2(μ-CH=CH-CH=CH-C6H4-CH=CH-CH=CH) was obtained from the reaction of [TpRu(CH=CHCH2PPh3)(CO)(PPh3)]BPh4 with NaN(SiMe3)2 and terephthaldicarboxaldehyde.

Reaction of cis-1, 4-dichlorobut-2-ene with dicyclohexylphosphine in the presence of KI in acetone produces [cis-Cy2PHCH2CH=CHCH2PHCy2]I2, which is converted to cis-Cy2PCH2CH=CHCH2PCy2 on treatment with NaOH. Reactions of cis-Cy2PCH2CH=CHCH2PCy2 with MHCl(CO)(PPh3)3(M=Ru, Os)yield MHCl(CO)(PPh3)(Cy2PCH2CH=CHCH2PCy2). The ruthenium complex RuCl(CO)(PPh3)(Cy2PCH2CH(CH2)2PCY2) is obtained by refluxing RuHCl(CO)(PPh3)(Cy2PCH2CH=CHCH2PCy2) in methanol-CH2Cl2. Reaction of RuCl(CO)(PPh3)(Cy2PCH2CH(CH2)2PCy2) with H2 in the presence of NaBPh4 produces RuHCl(CO)(PPh3)(Cy2P(CH2)4PCy2). Reaction of OsCl(PPh3)(2,6-(Ph2PCH2)2C6H3) with H2 produces OsCl(H...H)(PPh3(2,6-(Ph2PCH2)2C6H3) which contains an elongated dihydrogen ligand.

Reactions of HC=CCH2CH(OR)CH(OR)CH2C=CH(R=HMeSO2) with RuHCl(CO)(PPh2)3 produced [RuCl(CO)(PPh3)2]2(μ-CH=CHCH2CH(OR)CH(OR)CH2CH=CH). which on treat-ment with PMe3 gave [RuCl(CO)(PMe3)3]2(μ-CH=CHCH2CH(OR)CH(OR)CH2CH=CH). Treat-ment of RuHCl(CO)(PPh3)3 with (3E, 5E)-HC=CCH=CHCH=CHC=CH produced [RuCl-(CO)(PPh3)2]2(μ-CH=CHCH==CHCH=CHCH=CH). The later complex reacted with PMe3, 4-phenylpyrldine (PhPy), and 2, 6-(Ph2PCH2)2C5H3N (PMP) to give [RuCl(CO)(PMe3)3]2(μ-ch=chch=chch=chch=ch), [RuCl(CO)(PhPy)(PPh2)2]2(μ-CH=CHCH=CHCH=CHCH=CH), and [RuCl(CO)(PMP)]2(μ-CH=CHCH=CHCH=CHCH=CH). respectively. The struc-tures of RuCl(CO)(PMe3)3]2(μ-CH=CHCH2CH(OH)CH(OH)CH2CH=CH) and [RuCL(CO)(PMe3)32-(μ-CH=CHCH=CHCH=CHCH=CH) have been confirmed by X-ray diffraction.

Summary [Cp*Ru(H2O)(NBD)]BF4 reacted with H2 in benzene to give [Cp*Ru(η6-C6H6)]BF4 with H2 a formal [2+2+2] homo-Diels-Alder cycloaddition of MeC=CPh to NBD occurred when [Cp*Ru(H2O)(NBD)]-BF4 was treated with MeC=CPh. In contrast. An un-usual coupling product. which is formed by a formal addition of a C-H bond of styrene across one of the double bonds of NBD. was produced when [Cp*Ru(H2O)-(NBD)]BF4 was treated with CH2=CHPh.

The complex FC(CH=CH)2C=C-TMS(Fc=ferrocenyl)was obtained from Wittig olefination of FcCH2PPh3Br with TMS-C=CCH-CHCHO in THF. The conjugated monometallic dienecan be desilylated to give Fc(CH=CH)2C=CH, which reacted with RuHCl(CO)(PPh3)3 to produce Fc(CH=CH)3RuCl(CO)(PPh3)2. Treatment of the latter complex with PMe3, 4-phe-nylpyridine (PhPy), 2, 6-(Ph2PCH2)2C3H3N (PMP)2 and KTp (Tp-hydridotris(pyrazolyl)=bprate) gave Fc(CH=CH)3RuCl(CO)(PMe3)3RuCl(CO)(PhPy)(PPh3)2. Fc(CH=CH)3RuCl(CO)(PMP), and Fc(CH=CH)3RuTp(CO)(PPh3), respectively. The structures of Fc(CH=CH)2C=CH and Fc(CH=CH)3RuCl(CO)(PMe3)3 have been confirmed by X-ray diffraction.