GROUP-IB ORGANOMETALLIC CHEMISTRY .32. ARYLCOPPER COMPOUNDS ARNCUN AS INTERMEDIATES IN ORGANOMETALLIC SYNTHESIS - SINGLE-STEP SYNTHESIS AND DYNAMIC NMR-SPECTROSCOPY OF DIORGANOTIN DIHALIDES AR2-NRNSNX2(AR=2-ME2NCH2C6H4 OR (S)-2-ME2NCHMEC6H4-N=0 OR 1)

被引:47
作者
VANKOTEN, G [1 ]
JASTRZEBSKI, JTBH [1 ]
NOLTES, JG [1 ]
机构
[1] INST ORGAN CHEM TNO,NL-3522 AD UTRECHT,NETHERLANDS
关键词
D O I
10.1016/S0022-328X(00)92354-4
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The selective, single-step synthesis of (2-Me2NCHZC6H4)RSnX2, in which Z H or Me, R Me or Ph and X Cl or Br, starting from the tetranuclear copper cluster compound (2-Me2NCHZC6H4)4Cu4 and RSnX3 is described. Reaction of (2-Me2NCH2C6H4)4Cu4 with SnBr4 in a 1/2 molar ratio afforded (2-Me2NCH2C6H4)2SnBr2 in almost quantitative yield. 1H NMR spectroscopic data of these novel compounds, which are monomeric in solution, indicate that: (i) intramolecular SnN coordination renders the Sn atom in (2-Me2NCHZC6H4)RSnX2 pentacoordinate, with the organo ligands residing in the equatorial plane of a trigonal bipyramidal structure, and the Sn atom in (2-Me2NCH2C6H4)2SnBr2 hexacoordinate, with trans organo groups and a cis arrangement for the Br and the N atoms; (ii) in pyridine the Sn atom in (2-Me2NCHZC6H4)RSnX2 becomes hexacoordinate by complex formation with the solvent but that intramolecular SnN coordination has been retained. The stereochemical lability of the pentacoordinate Sn center in the diorganotin dihalides (2-Me2NCHZC6H4)RSnX2, which contain a dissymmetrical equatorial plane, has been established on the basis of the dynamic NMR spectra of. © 1979.
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页码:283 / 292
页数:10
相关论文
共 24 条
[1]  
BARBIERI R, UNPUBLISHED
[2]   THERMODYNAMICS OF METAL-LIGAND BOND FORMATION .16. BASE ADDUCTS OF SOME ORGANOTIN COMPOUNDS [J].
FARHANGI, Y ;
GRADDON, DP .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1975, 87 (01) :67-82
[3]   ORGANOMETALLIC COMPOUNDS .54. MECHANISM EXPLAINING CONFIGURATIONAL INSTABILITY OF TRIORGANOTIN HALIDES [J].
GIELEN, M ;
MOKHTARJAMAI, H .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1977, 129 (03) :325-330
[4]   STRUCTURAL STUDIES IN MAIN GROUP CHEMISTRY .11. TIN-119M MOSSBAUER INVESTIGATIONS OF TRIORGANOTIN DERIVATIVES OF SUBSTITUTED PYRIDINES [J].
HARRISON, PG ;
PHILLIPS, RC .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1975, 99 (01) :79-91
[5]   STRUCTURAL ORGANOTIN CHEMISTRY [J].
HO, BYK ;
ZUCKERMA.JJ .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1973, 49 (01) :1-84
[6]   SPECTROSCOPY AND STRUCTURE OF PENTACOORDINATED MOLECULES [J].
HOLMES, RR .
ACCOUNTS OF CHEMICAL RESEARCH, 1972, 5 (09) :296-&
[7]  
KUMARDAS VG, 1976, J INORG NUCL CHEM, P1241
[8]   SOLVENT-INDUCED ISOMERIZATION OF HALOSILACYCLOBUTANES - MECHANISM WITH IONIC INTERMEDIATES WITH EXPANDED COORDINATION [J].
MCKINNIE, BG ;
CARTLEDGE, FK .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1976, 104 (03) :407-411
[9]   PENTACO-ORDINATION [J].
MUETTERTIES, EL ;
SCHUNN, RA .
QUARTERLY REVIEWS, 1966, 20 (02) :245-+
[10]  
Petrosyan V S, 1976, ADV ORGANOMET CHEM, V14, P63