Synthesis and Crystal Structure of the Novel Dianion [Re(CO)3(5-7-CB10H11)]2
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- 作者：Ian Blandford ; John C. Jeffery ; Paul A. Jelliss ; and F. Gordon A. Stone
- 刊名：Organometallics
- 出版年：1998
- 出版时间：March 30, 1998
- 年：1998
- 卷：17
- 期：7
- 页码：1402 - 1411
- 全文大小：168K
- 年卷期：v.17,no.7(March 30, 1998)
- ISSN：1520-6041
文摘
The salts[X]2[Re(CO)3(
5-7-CB10H11)](X = N(PPh3)2 (2a), X =NEt3(CH2Ph) (2b))havebeen 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-raydiffraction study revealedthat 2b crystallizes in the orthorhombic space groupPna21. The anion of 2a could notbeoxidized by a host of oxidants with the exception of I2,which yielded the salt[N(PPh3)2][ReI(CO)3(5-7-CB10H11)](3). The neutral bimetallic complexes[RePt(CO)3(L)2(5-7-CB10H11)](L = PPh3 (4a), L = PEt3(4b), (L)2 =Ph2P(CH2)2PPh2(4c)) have been prepared by treating2a in THF with [PtCl2(L)2] inthe presence of TlPF6. X-ray diffraction revealed thatcompound4a crystallizes in the monoclinic space groupC2/c. The molecule contains a bridgingnido-7-CB10H11 ligand which is5-coordinated to the Re atom and is bound to the Pt atomby aB
-H
Pt agostic bond. The compound[RePd(CO)3{Ph2P(CH2)2PPh2}(5-7-CB10H11)](5a) hasbeen prepared by treating 2a with[PdCl2{Ph2P(CH2)2PPh2}]in THF in the presence of TlPF6.X-ray diffraction showed that 5a crystallizes in theorthorhombic space groupP212121,andthe structure in the solid-state is similar to that of 4abut with a B-HPd agostic bond. Insolution, an exchange occurs on the NMR time scale between the B-Hbonds in thecoordinating 43a10001">CBBB B face which form the B-HPdlinkage, thus generating a pseudo planeof symmetry in the molecule. Treatment ofCH2Cl2 solutions of 5a with CNR(R = But,C6H3Me2-2,6) at -78 
Cyields the complexes[RePd(CO)2(CNR){Ph2P(CH2)2PPh2}(5-7-CB10H11)] (R = But(5b), R =C6H3Me2-2,6 (5c)).The IR and NMR spectra of the newcompounds are discussed.
5-7-CB10H11)](X = N(PPh3)2 (2a), X =NEt3(CH2Ph) (2b))havebeen 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-raydiffraction study revealedthat 2b crystallizes in the orthorhombic space groupPna21. The anion of 2a could notbeoxidized by a host of oxidants with the exception of I2,which yielded the salt[N(PPh3)2][ReI(CO)3(5-7-CB10H11)](3). The neutral bimetallic complexes[RePt(CO)3(L)2(5-7-CB10H11)](L = PPh3 (4a), L = PEt3(4b), (L)2 =Ph2P(CH2)2PPh2(4c)) have been prepared by treating2a in THF with [PtCl2(L)2] inthe presence of TlPF6. X-ray diffraction revealed thatcompound4a crystallizes in the monoclinic space groupC2/c. The molecule contains a bridgingnido-7-CB10H11 ligand which is5-coordinated to the Re atom and is bound to the Pt atomby aB-HPt agostic bond. The compound[RePd(CO)3{Ph2P(CH2)2PPh2}(5-7-CB10H11)](5a) hasbeen prepared by treating 2a with[PdCl2{Ph2P(CH2)2PPh2}]in THF in the presence of TlPF6.X-ray diffraction showed that 5a crystallizes in theorthorhombic space groupP212121,andthe structure in the solid-state is similar to that of 4abut with a B-HPd agostic bond. Insolution, an exchange occurs on the NMR time scale between the B-Hbonds in thecoordinating Pdlinkage, thus generating a pseudo planeof symmetry in the molecule. Treatment ofCH2Cl2 solutions of 5a with CNR(R = But,C6H3Me2-2,6) at -78 Cyields the complexes[RePd(CO)2(CNR){Ph2P(CH2)2PPh2}(5-7-CB10H11)] (R = But(5b), R =C6H3Me2-2,6 (5c)).The IR and NMR spectra of the newcompounds are discussed.