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В результате присоединения [CuCl] и [Fe(CO)4] к винилиденовому комплексу рения Cp(CO)2Re=C=CHPh (1) получены новые гетероядерные комплексы [Cp(CO)2ReCu( -C=CHPh) ( -Cl)]2 (2) и Cp(CO)2ReFe( -C=CHPh)(CO)4 (3). Строение соединений (2) и (3) предложено на основании данных спектров ИК и ЯМР и предполагает наличие мостикового лиганда -C=CHPh над связями Re-Cu и Re-Fe соответственно. Изучено химическое поведение комплекса (2) в реакциях с PPh3 и Fe2(CO)9. Проведено сопоставление полученных результатов с данными для ранее изученных родственных соединений марганца. The additions of the Cu- and Fe-containing unsaturated fragments to the vinylidene complex Cp(CO)2Re=C=CHPh (1) afforded new binuclear complexes [Cp(CO)2ReCu( -C=CHPh)- ( -Cl)]2 (2) and Cp(CO)2ReFe( -C=CHPh)(CO)4 (3). Molecular constitution of the compounds 2 and 3 were proposed from IR and NMR spectroscopy data and confirmed the presence of the -C=CHPh ligand bridging the Re-Cu and Re-Fe bonds, correspondingly. The chemical behavior of complex 2 towards action of PPh3 and Fe2(CO)9 has been investigated. The results obtained were compared with data for relative manganese complexes previously studied.

При взаимодействии Cp(CO)2Re=C=CHPh (1) с Pt(PPh3)4 получен μ-винилиденовый комплекс Cp(CO)2RePt(μ-C=CHPh)(PPh3)2 (2). Исследованы спектры ИК и ЯМР 1Н, 13С и 31P соединения 2. Кристаллическая и молекулярная структура комплекса 2 установлена методом РСА [длины связей Re—Pt 2.7360(3), Re—C1 2.083(5), Pt—C1 2.008(4), C1=C2 1.351(6) Å; валентные углы Pt-C1-C2 133.5(4), Re-C1-C2 141.6(4)°]. Обсуждается влияние природы атома металла M = Re, Mn на структурные и спектральные характеристики комплексов Cp(CO)2MPt(μ-C=CHPh)(PPh3)2., The interaction between Cp(CO)2Re=C=CHPh (1) and Pt(PPh3)4 afforded the μ-vinylidene complex Cp(CO)2RePt(μ-C=CHPh)(PPh3)2 (2). The IR and 1H, 13C and 31P NMR spectra of complex 2 were studied. Crystal and molecular structure of complex 2 has been determined by an X-ray single crystal analysis. The bond distances and angles are Re—Pt 2.7360(3), Re—C1 2.083(5), Pt—C1 2.008(4), C1=C2 1.351(6) Å; Pt-C1-C2 133.5(4), Re-C1-C2 141.6(4)°. The influence of the nature of the M = Re, Mn atoms on structural and spectroscopic characteristics of complexes Cp(CO)2MPt(μ-C=CHPh)-(PPh3)2 has been considered.

In this work a facile route to arylvinylidene complexes of chromium and tungsten with a broad variability with respect to substituents and ligands was developed. The influence of various structural parameters on the reactivity of these complexes towards alkynes, ynamines and alkoxyacetylenes was determined. The four-membered NHC ligands obtained by addition of imines to vinylidene ligands could be transferred from tungsten and chromium to catalytic active metals like palladium and gold. This represents a route to new catalysts for homogenous catalysis.

The reaction of the vinylidene complex [(eta(5)-C5H5)(CO)(NO)-W=C=C(H)Ph] (9) with the phosphaalkenes RP=C(NMe2)(2) (1a: R=tBu; 1c: R=c-C6H11) affords the novel eta(2)-1-phosphaallene complexes [eta(2)-{RP=C=C(H)Ph}W(CO)(NO)(eta(5)-C5H5)] (14: R=tBu; 15: R=c-C6H11) in addition to the carbene complex [(eta(5)-C5H5)(CO)(NO)W=C(NMe2)C(Ph)=C(H)NMe2] (16). Similarly, treatment of [(eta(5)-C5H5)(CO)(NO)W=C=CH2] (12) with the phosphaalkenes gives rise to the formation of [eta(2)-{RP=C=CH2})W(CO)(NO)(eta(5)-C5H5)] (17: R=tBu; 18: R=c-C6H11. The novel compounds 14, 15, 17, and 18 were characterized by elemental analysis and by spectroscopy (IR, H-1, C-13 NMR, MS). Moreover, the molecular structures of 14 and 16 were determined by X-ray diffraction analyses. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

The reaction of the vinylidene complexes [(C5H5)(CO)(NO)W=C=C(H)RI (10a: R = tBu; 10b: R = Ph) with the arsaalkene tBuC(O)-As=C(NMe2)(2) (11) afforded the novel eta(2)-1-arsaallene complexes [eta(2)-{tBuC(O)-As=C=C(H)R}W(CO)(NO)-C5H5] (13: R = tBu; 15: R = Ph). Similarly, treatment of 10a with the ferrioarsaalkene [(C5Me5)(CO)(2)Fe-As=C(NMe2)(2)] (12) led to the formation of [eta(2)-{[(C5Me5)(CO)(2)Fe]-As=C=C(H)tBu}W(CO)(NO)(C5H5)] (14), whereas combination of 12 and 1 Ob yielded the carbene complex [(C5H5) (CO) (NO)W=C(NMe2)C(Ph)=C(H)NMe2] (16) in high yield instead of the anticipated arsaallene complex. The novel compounds 13, 14, 15 and 16 were characterised by elemental analyses and by means of spectroscopy (IR, H-1, C-13 NMR). Moreover, the molecular structures of 14 and 15 were elucidated by X-ray diffraction analyses. (c) Wiley-VCH Verlag GmbH & Co. KGaA.

Thermolysis of the pentacarbonyl(vinylidene)chromium complexes [(CO)5CrCC(R1)R2] (1a–d) (C(R1)R2=CMe2 (a), C(CH2)5 (b), C(Et)Me (c), C(tBu)Me (d)), affords binuclear, vinylidene-bridged nonacarbonyldichromium complexes, [(CO)5Cr(μ-η1,η2-CC(R1)R2)Cr(CO)4] (2a–d). The solid-state structures of 2a and 2d have been established by X-ray structural analyses. The structural data prove the μ-η1,η2-CC(R1)R2 bonding mode. To account for the NMR spectroscopic features a dynamic process is proposed involving rapid coordination site exchange of the CC bond between Cr(1) and Cr(2) (windshield wiper mechanism) and of one CO ligand.