Two Successive Steps of Hypercoordination at Tin: The Gas-Phase and Solid-State Structures of (N,N-Dimethylaminoxy)trimethylstannane

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• 作者：Norbert W. Mitzel ; Udo Losehand ; and Alan Richardson
• 刊名：Organometallics
• 出版年：1999
• 出版时间：July 5, 1999
• 年：1999
• 卷：18
• 期：14
• 页码：2610 - 2614
• 全文大小：62K
• 年卷期：v.18,no.14(July 5, 1999)
• ISSN：1520-6041

文摘

Me₃SnONMe₂ has been prepared from trimethyltin chloride and O-lithio-N,N-dimethylhydroxylamine and characterized by IR and NMR spectroscopy, mass spectrometry, andelemental analysis. Its gas-phase molecular structure has been determined by electrondiffraction augmented by restraints taken from ab initio calculations at the MP2/DZ(P) levelof theory. A secondary interaction (Sn···N, 2.731(14) Å) between the tin and nitrogen atomshas been detected and makes Me₃SnONMe₂ the first partially hypercoordinate tin compoundstudied in the gas phase. A solid-state structure of Me₃SnONMe₂ has been determined byX-ray diffraction of an in situ grown single crystal. In the crystal lattice the coordinationsphere of tin is further enlarged by a weak intermolecular Sn···O contact (2.998(10) Å) anda 4+2 coordination geometry is achieved, which can be deduced from that of a distortedtrigonal bipyramid with one of the axial substituents replaced by the two weak contacts.Important geometry parameter values are as follows (gas/solid): Sn-O 2.006(3)/2.063(6) Å,O-N 1.468(6)/1.440(9) Å, Sn-C(in plane) 2.148(4)/2.163(14) Å, Sn-C(out of plane) 2.146(3)/2.062(9) and 2.185(10) Å, Sn-O-N 102.5(8)/101.5(4)es/entities/deg.gif">, O-Sn-C(in plane) 99.6(10)/99.7(4)es/entities/deg.gif">,O-Sn-C(out of plane) 108.1(6)/119.6(4)es/entities/deg.gif"> and 116.6(4)es/entities/deg.gif">.