Synthesis and Crystal Structure of the Novel Dianion [Re(CO)3(η5-7-CB10H11)]2-. Reactions with Platina- and Palladaphosphine Chlorides

The salts [X]2[Re(CO)3(η5-7-CB10H11)] (X = N(PPh3)2 (2a), X = NEt3(CH2Ph) (2b)) have been synthesized from the reaction between [Na]3[nido-7-CB10H11] and [ReBr(THF)2(CO)3] (THF = tetrahydrofuran) followed by addition of XCl. An X-ray diffraction study revealed that 2b crystallizes in the orthorhombic space group Pna21. The anion of 2a could not be oxidized by a host of oxidants with the exception of I2, which yielded the salt [N(PPh3)2][ReI(CO)3(η5-7-CB10H11)] (3). The neutral bimetallic complexes [RePt(CO)3(L)2(η5-7-CB10H11)] (L = PPh3 (4a), L = PEt3 (4b), (L)2 = Ph2P(CH2)2PPh2 (4c)) have been prepared by treating 2a in THF with [PtCl2(L)2] in the presence of TlPF6. X-ray diffraction revealed that compound 4a crystallizes in the monoclinic space group C2/c. The molecule contains a bridging nido-7-CB10H11 ligand which is η5-coordinated to the Re atom and is bound to the Pt atom by a Bβ-H⇀Pt agostic bond. The compound [RePd(CO)3{Ph2P(CH2)2PPh2}(η5-7-CB10H11)] (5a) has been prepared by treating 2a with [PdC...