New type of reactions of stannylenes with organic azides: Theoretical study

被引：6

作者：

Nechaev, Mikhail S. ^{[1
,2
]}

机构：

[1] Moscow MV Lomonosov State Univ, Dept Chem, Moscow 119991, Russia

[2] Russian Acad Sci, AV Topchiev Petrochem Synth Inst, Moscow 119991, Russia

来源：

JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM | 2008年 / 862卷 / 1-3期

基金：

俄罗斯基础研究基金会;

关键词：

reaction mechanism; potential energy surface; stannylene; tin azide; stannaimine;

D O I：

10.1016/j.theochem.2008.04.024

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Density functional study of the reaction of Sn(OCH2CH2NMe2)(2) (1) with Me3Si-N-3 (2) yielding the redistribution product [(N-3)SnOCH2CH2NMe2](2) (3) has been performed at the PBE/TZ2P(SBKJC) level. Two possible reaction paths, the formation of [(N-3)SnOCH2CH2NMe2](2) (path A) and initially expected imine Me3Si-N=Sn(OCH2CH2NMe2)(2) (5) (path B), have been studied. The formation of the imine 5 is thermally more favorable than the formation of dimeric stannylene 3, Delta G(0)(5) = -6.7 kcal/mol and Delta G(0)(3) = -5.9 kcal/mol. The reaction proceeds to 3 due to a lower energy barrier, Delta G(double dagger) = 27.8 and 39.5 kcal/mol for 3 and 5, respectively. (C) 2008 Elsevier B.V. All rights reserved.

引用

页码：49 / 52

页数：4

共 33 条

[21] REACTIONS OF BIS[BIS(TRIMETHYLSILYL)METHYL]GERMYLENE AND THE CORRESPONDING STANNYLENE WITH DIAZIDOSILANES
OHTAKI, T
KABE, Y
ANDO, W
[J]. HETEROATOM CHEMISTRY, 1994, 5 (03) : 313 - 320
[22] Perdew JP, 1997, PHYS REV LETT, V78, P1396, DOI 10.1103/PhysRevLett.77.3865
[23] REACTIONS OF GERMYLENES WITH AZIDES - IMINOGERMANES, AZIDOGERMANES, TETRAZAGERMOLES, AND HEXAAZADIGERMADISPIRODODECANES
PFEIFFER, J
MARINGGELE, W
NOLTEMEYER, M
MELLER, A
[J]. CHEMISCHE BERICHTE, 1989, 122 (02) : 245 - 252
[24] Portmann S., 2002, MOLEKEL VERSION 4 3
[25] An unusual reaction of (β-dimethylaminoethoxy)triethyltin with phenyltin trichloride.: The first X-ray structural evidence of the existence of complexes R2SnXY•R2SnXY (R = alkyl, aryl;: X, Y = Hal, OR, X ≠ Y) both as unsymmetrical adducts [R2SnX2•R2SnY2] and symmetrical dimers [R2SnXY]2
Portnyagin, Ivan A.
Nechaev, Mikhail S.
Khrustalev, Victor N.
Zemlyansky, Nikolay N.
Borisova, Irina V.
Antipin, Mikhail Yu.
Ustynyuk, Yuri A.
Lunin, Valery V.
[J]. EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 2006, (21) : 4271 - 4277
[26] N-MESITYLDIMESITYLGERMAIMINE
RIVIEREBAUDET, M
SATGE, J
MORERE, A
[J]. JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1990, 386 (01) : C7 - C11
[27] SnCl2 mediated efficient N,N-dialkylation of azides to tertiary-amine via potential stannaimine intermediate
Roy, UK
Roy, S
[J]. JOURNAL OF ORGANOMETALLIC CHEMISTRY, 2006, 691 (08) : 1525 - 1530
[28] COMPACT EFFECTIVE POTENTIALS AND EFFICIENT SHARED-EXPONENT BASIS-SETS FOR THE 1ST-ROW AND 2ND-ROW ATOMS
STEVENS, WJ
BASCH, H
KRAUSS, M
[J]. JOURNAL OF CHEMICAL PHYSICS, 1984, 81 (12) : 6026 - 6033
[29] RELATIVISTIC COMPACT EFFECTIVE POTENTIALS AND EFFICIENT, SHARED-EXPONENT BASIS-SETS FOR THE 3RD-ROW, 4TH-ROW, AND 5TH-ROW ATOMS
STEVENS, WJ
KRAUSS, M
BASCH, H
JASIEN, PG
[J]. CANADIAN JOURNAL OF CHEMISTRY-REVUE CANADIENNE DE CHIMIE, 1992, 70 (02): : 612 - 630
[30] Synthesis of cyclic, chiral compounds including Ge-El double bonds (El=N, S, (O)) and their dynamic behaviour in solution
Veith, M
Rammo, A
[J]. ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE, 1997, 623 (05): : 861 - 872

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