SYNTHESIS AND DYNAMIC BEHAVIOR OF (PENTAMETHYLCYCLOPENTADIENYL)AZATANTALACYCLOPROPANE COMPLEXES - CRYSTAL-STRUCTURES OF TACP-ASTERISK-CL-4[C(ME)(NHR)] AND TACP-ASTERISK-ME(2)(ETA(2)-ME(2)CNR)

被引：58

作者：

GALAKHOV, MV ^{[1
]}

GOMEZ, M ^{[1
]}

JIMENEZ, G ^{[1
]}

ROYO, P ^{[1
]}

PELLINGHELLI, MA ^{[1
]}

TIRIPICCHIO, A ^{[1
]}

机构：

[1] UNIV PARMA, CNR, CTR STUDIO STRUTTURIST DIFFRATTOMETR, I-43100 PARMA, ITALY

来源：

ORGANOMETALLICS | 1995年 / 14卷 / 04期

关键词：

D O I：

10.1021/om00004a050

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The amino carbene adducts TaCp*Cl-4[C(Me)NHR)] (R = 2,6-Me(2)C(6)H(3), 1a; 2,4,6-Me(3)C(6)H(2), 1b) have been prepared by reaction with HCl of solutions containing the acylimidoyl complexes TaCp*Cl-3(eta(2)-MeC=NR) prepared by addition of isocyanides CNR to TaCp*Cl(3)Me. Solutions of pure acylimidoyl derivatives can be prepared and characterized in sealed tubes or in a drybox, as they are very easily hydrolyzed in the presence of traces of water. Reaction of TaCp*Cl(2)Me(2) with 1 equiv of isocyanides takes place with double migration of methyl, leading to the formation of azatantalacyclopropane complexes TaCp*Cl-2(eta(2)-Me(2)CNR) (R = 2,6-Me(2)C(6)H(3), 2a; 2,4,6-Me(3)C(6)H(2), 2b). Complexes 2 are easily protonated by HCl to give aryl isopropyl amido derivatives TaCp*Cl-3(N(i)PrR) (R = 2,6-Me(2)C(6)H(3), 3a; 2,4,6-Me(3)C(6)H(2), 3b), which decompose at 120 degrees C with evolution of isopropyl chloride to give the imido complexes TaCp*Cl-2(NR) (R = 2,6-Me(2)C(6)H(3), 4a; 2,4,6-Me(3)C(6)H(2), 4b). Methylation of 2a with 2 equiv of LiMe gives TaCp*Me(2)[eta(2)-Me(2)CN(2,6-Me(2)C(6)H(3))] (5a), which alternatively can be obtained by reaction of 3a with 3 equiv of MgClMe with evolution of methane. All the complexes isolated were studied by IR and H-1, C-13 NMR spectroscopy. The dynamic behavior of 2a and 5a was studied in solution between 203 and 303 K, and kinetic parameters were determined. The crystal structures of 1a and 5a were determined by X-ray diffraction methods. Crystals of the benzene solvate of la are triclinic, space group P-1 with Z = 2 in a unit cell of dimensions a = 8.381(4) Angstrom, b = 8.977(4) Angstrom, c = 18.316(9) Angstrom, alpha = 100.17(2)degrees, beta = 97.83(2)degrees, and y = 105.04(2)degrees. Crystals of 5a are monoclinic, space group P2(1)/n with Z = 4 in a unit cell of dimensions a = 10.515(6) Angstrom, b = 14.615(9) Angstrom, c = 14.594(8) Angstrom, and beta = 100.66(2)degrees. Both structures were solved from diffractometer data by Patterson and Fourier methods and refined by full-matrix least-squares fit on the basis of 3218 (1a . 1/2C(6)H(6)) and 3786 (5a) observed reflections to R and Rw values of 0.0432 and 0.0534 (1a . 1/2C(6)H(6)) and 0.0299 and 0.0316 (5a), respectively.

引用

页码：1901 / 1910

页数：10

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