Reactions of Trimethylaluminum with Secondary Arsines: Synthesis and Characterization of Phenyl[(trimethylsilyl)methyl]arsine and the X-ray Crystal Structures of the Trimers [Me2AlAsPh
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- 作者：Janeen A. Laske Cooke ; Andrew P. Purdy ; Richard L. Wells ; and Peter S. White
- 刊名：Organometallics
- 出版年：1996
- 出版时间：January 9, 1996
- 年：1996
- 卷：15
- 期：1
- 页码：84 - 90
- 全文大小：223K
- 年卷期：v.15,no.1(January 9, 1996)
- ISSN：1520-6041
文摘
The reactions of trimethylaluminum with diphenylarsine,Ph2AsH, and phenyl[(trimethylsilyl)methyl]arsine,Ph(Me3SiCH2)AsH, in 1:1 mole ratiosafford the trimeric compounds[Me2AlAsPh2]3·(C7H8)2(1) and[Me2AlAs(CH2SiMe3)Ph]3(2), respectively. Compounds 1and2 are the first Al-As six-membered-ring compounds to bestructurally characterized by single-crystal X-ray crystallography, as well as by 1H and13C solution NMR spectroscopy. X-raycrystallographic analysis revealed that trimer 1 is atoluate that crystallizes in the monoclinicspace group P21/n, with a= 14.549(6) Å, b = 22.838(7) Å, c= 16.891(4) Å, and 
chars/beta2.gif" BORDER=0 ALIGN="middle"> = 105.12(5)
for Z = 4. Trimer 2 crystallizes in thetriclinic system, space group P
, and has twouniquemolecules in a unit cell with dimensions of a =15.619(7) Å, b = 17.487(6) Å, c =19.863(6)Å, chars/alpha.gif" BORDER=0> = 94.86(3), chars/beta2.gif" BORDER=0 ALIGN="middle"> = 101.41(3), and chars/gamma.gif" BORDER=0 > =113.34(3) for Z = 4. The six-memberedAl-Asrings in both 1 and 2 occupy chair conformations,furnishing both trimers with structuralcharacteristics similar to those of cyclohexane. The Al and Ascenters of both 1 and 2 residein pseudotetrahedral environments, with the Al-As bond lengthsranging from 2.512(3) to2.542(3) Å in 1 and from 2.504(5) to2.526(5) Å in 2.
chars/beta2.gif" BORDER=0 ALIGN="middle"> = 105.12(5)for Z = 4. Trimer 2 crystallizes in thetriclinic system, space group P, and has twouniquemolecules in a unit cell with dimensions of a =15.619(7) Å, b = 17.487(6) Å, c =19.863(6)Å, chars/alpha.gif" BORDER=0> = 94.86(3), chars/beta2.gif" BORDER=0 ALIGN="middle"> = 101.41(3), and chars/gamma.gif" BORDER=0 > =113.34(3) for Z = 4. The six-memberedAl-Asrings in both 1 and 2 occupy chair conformations,furnishing both trimers with structuralcharacteristics similar to those of cyclohexane. The Al and Ascenters of both 1 and 2 residein pseudotetrahedral environments, with the Al-As bond lengthsranging from 2.512(3) to2.542(3) Å in 1 and from 2.504(5) to2.526(5) Å in 2.