Synthesis, Structure, and DFT Calculation of (Phosphino-o-carboranyl)silyl Group 10 Metal Complexes: Formation of Stable trans-Bis(P,Si-chelate)metal Complexes
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- 作者：Young-Joo Lee ; Jong-Dae Lee ; Sung-Joon Kim ; Samrok Keum ; Jaejung Ko ; Il-Hwan Suh ; Minserk Cheong ; and Sang Ook Kang
- 刊名：Organometallics
- 出版年：2004
- 出版时间：January 19, 2004
- 年：2004
- 卷：23
- 期：2
- 页码：203 - 214
- 全文大小：317K
- 年卷期：v.23,no.2(January 19, 2004)
- ISSN：1520-6041
文摘
Addition of the silane (HSiMe2)C2B10H10(PR2) (R = Me (2a), OEt (2b)) to (PPh3)2Pt(CH2CH2) (3) affords the trans-bis(chelates) Pt(CabP,Si)2 (4a,b; CabP,Si = 
2-[(SiMe2)(PR2)C2B10H10-P,Si]) in high yield; the same product was also formed from Pt(cod)2 (9), as confirmed byNMR spectroscopy (1H, 31P). Using Pd2(dba)3 (6), the analogue trans-bis(chelate) Pd(CabP,Si)2(7a) was obtained as a mixture of trans and cis isomers in which the former predominates,as established by NMR spectroscopy (1H, 31P). Thus, a series of kinetically stabilized trans-bis(chelate) metal complexes, trans-(CabP,Si)2M (M = Pt (4a,b), Pd (7a)), bearing bulkyo-carboranylphosphine tethers, were synthesized from the reaction of phosphinosilanes (2)with d10 metal complexes. In the presence of dimethyl acetylenedicarboxylate (DMAD), thetrans isomer 4a,b thermally rearranges to the thermodynamically favored cis isomer cis-(CabP,Si)2Pt (5a,b). In addition, the oxidative addition of the Si-H bond to the stericallybulky diphenylphosphino silane (HSiMe2)C2B10H10(PPh2) (2c) by 3 can be controlled toproduce the mono(chelate) species (CabP,Si)Pt(H)(PPh3) (10a). The related mono(chelate)product (CabP,Si)Pt(H)(CabP) (10b; CabP = (PPh2)C2B10H11) results from the oxidative additionof 2c by 3, in which one PPh3 ligand is displaced by CabP. The structures of compounds 4a,5a,c, 8c, and 10a,b were determined using single-crystal X-ray crystallography.
2-[(SiMe2)(PR2)C2B10H10-P,Si]) in high yield; the same product was also formed from Pt(cod)2 (9), as confirmed byNMR spectroscopy (1H, 31P). Using Pd2(dba)3 (6), the analogue trans-bis(chelate) Pd(CabP,Si)2(7a) was obtained as a mixture of trans and cis isomers in which the former predominates,as established by NMR spectroscopy (1H, 31P). Thus, a series of kinetically stabilized trans-bis(chelate) metal complexes, trans-(CabP,Si)2M (M = Pt (4a,b), Pd (7a)), bearing bulkyo-carboranylphosphine tethers, were synthesized from the reaction of phosphinosilanes (2)with d10 metal complexes. In the presence of dimethyl acetylenedicarboxylate (DMAD), thetrans isomer 4a,b thermally rearranges to the thermodynamically favored cis isomer cis-(CabP,Si)2Pt (5a,b). In addition, the oxidative addition of the Si-H bond to the stericallybulky diphenylphosphino silane (HSiMe2)C2B10H10(PPh2) (2c) by 3 can be controlled toproduce the mono(chelate) species (CabP,Si)Pt(H)(PPh3) (10a). The related mono(chelate)product (CabP,Si)Pt(H)(CabP) (10b; CabP = (PPh2)C2B10H11) results from the oxidative additionof 2c by 3, in which one PPh3 ligand is displaced by CabP. The structures of compounds 4a,5a,c, 8c, and 10a,b were determined using single-crystal X-ray crystallography.