共查询到10条相似文献,搜索用时 375 毫秒
1.
Alpar Pöllnitz Anca Silvestru Cristian Silvestru 《Journal of organometallic chemistry》2010,695(23):2486-2492
Diorganodiselenide [2-(Et2NCH2)C6H4]2Se2 (1) was obtained by hydrolysis/oxidation of the corresponding [2-(Et2NCH2)C6H4]SeLi derivative. The treatment of [2-(Et2NCH2)C6H4]2Se2 with elemental sodium in THF resulted in [2-(Et2NCH2)C6H4]SeNa (2). Reactions between alkali metal selenolates [2-(R2NCH2)C6H4]SeM′ (R = Me, Et; M′ = Li, Na) and MCl2 (M = Zn, Cd) in a 2:1 molar ratio resulted in the [2-(R2NCH2)C6H4Se]2M species [R = Me, M = Zn (3), Cd (4); R = Et, M = Zn (5), Cd (6)]. The new compounds were characterized by multinuclear NMR (1H, 13C, 77Se, 113Cd) and mass spectrometry. The crystal and molecular structures of 1, 3 and 4 revealed monomeric species stabilized by N → Se (for 1) and N → M (for 3 and 4) intramolecular interactions. 相似文献
2.
Miao-Hsing Hsu 《Journal of organometallic chemistry》2006,691(5):966-974
A facile synthesis of the novel selenium-capped trimolybdenum and tritungsten ring carbonyl clusters [Se2M3(CO)10]2− (M = Mo, 1; W, 4) have been achieved. The selenium-capped trimolybdenum cluster compound [Et4N]2[Se2Mo3(CO)10] ([Et4N]2[1]) can be obtained from the reaction of the trichromium cluster compound [Et4N]2[Se2Cr3(CO)10] with 4 equiv. of Mo(CO)6 in refluxing acetone. On the other hand, when [Et4N]2[Se2Cr3(CO)10] reacted with 4 equiv. of W(CO)6 in refluxing acetone, the planar cluster compound [Et4N]2[Se2W4(CO)18] ([Et4N]2[3]) was isolated, which could further transform to the tritungsten cluster compound [Et4N]2[Se2W3(CO)10] ([Et4N]2[4]) in good yield. Alternatively, clusters 1 and 4 could be formed from the reactions of the monosubstituted products [Et4N]2[Se2Cr2M(CO)10] (M = Mo; W, [Et4N]2[2]) with 3 equiv. of M(CO)6 in acetone, respectively. Complexes 1-4 are fully characterized by IR, 77Se NMR spectroscopy, and single-crystal X-ray analysis. Clusters 1, 2, and 4 are isostructural and each display a trigonal bipyramidal structure with a homometallic M3 ring (M = Mo, 1; W, 4) or a heterometallic Cr2W ring that is further capped above and below by μ3-Se atoms. Further, the intermediate planar complex 3 exhibits a Se2W2 square with each Se atom externally coordinated to one W(CO)5 group. This paper describes a systematic route to a series of selenium-capped trimetallic carbonyl clusters and the formation and the structural features of the resultant clusters are discussed. 相似文献
3.
Schiff base N,N′-bis(salicylidene)-p-phenylenediamine (LH2) complexed with Pt(en)Cl2 and Pd(en)Cl2 provided [Pt(en)L]2 · 4PF6 (1) and Pd(Salen) (2) (Salen = N,N′-bis(salicylidene)-ethylenediamine), respectively, which were characterized by their elemental analysis, spectroscopic data and X-ray data. A solid complex obtained by the reaction of hexafluorobenzene (hfb) with the representative complex 1 has been isolated and characterized as 3 (1 · hfb) using UV–Vis, NMR (1H, 13C and 19F) data. A solid complex of hfb with a reported Zn-cyclophane 4 has also been prepared and characterized 5 (4 · hfb) for comparison with complex 3. The association of hfb with 1 and 4 has also been monitored using UV–Vis and luminescence data. 相似文献
4.
Ph2SiCl2 and PhMeSiCl2 react with Li2E (E = S, Se, Te) under formation of trimeric diorganosilicon chalcogenides (PhRSiE)3 (R = Ph: 1a-3a, R = Me: cis/trans-4a (E = S), cis/trans-5a (E = Se)). In case of E = S, Se dimeric four-membered ring compounds (PhRSiE)2 (R = Ph: 1b-2b, R = Me: cis/trans-4b (E = S), cis/trans-5b (E = Se)) have been observed as by-products. 1a-5b have been characterized by multinuclear NMR spectroscopy (1H, 13C, 29Si, 77Se, 125Te). Four- and six-membered ring compounds differ significantly in 29Si and 77Se chemical shifts as well as in the value of 1JSiSe.The molecular structures of 2a, 3a and trans-5a reported in this paper are the first examples of compounds with unfused six-membered rings Si3E3 (E = Se, Te). The Si3E3 rings adopt twisted boat conformations. The crystal structure of 3a reveals an intermolecular Te-Te contact of 3.858 Å which yields a dimerization in the solid state. 相似文献
5.
Michael I. Bruce Marcus L. Cole Brian W. Skelton 《Journal of organometallic chemistry》2006,691(22):4601-4614
Complexes M(CCCSiMe3)(CO)2Tp′ (Tp′ = Tp [HB(pz)3], M = Mo 2, W 4; Tp′ = Tp∗ [HB(dmpz)3], M = Mo 3) are obtained from M(CCCSiMe3)(O2CCF3)(CO)2(tmeda) (1) and K[Tp′].Reactions of 2 or 4 with AuCl(PPh3)/K2CO3 in MeOH afforded M{CCCAu(PPh3)}(CO)2Tp′ (M = Mo 5, W 6) containing C3 chains linking the Group 6 metal and gold centres.In turn, the gold complexes react with Co3(μ3-CBr)(μ-dppm)(CO)7 to give the C4-bridged {Tp(OC)2M}CCCC{Co3(μ-dppm)(CO)7} (M = Mo 7, W 8), while Mo(CBr)(CO)2Tp∗ and Co3{μ3-C(CC)2Au(PPh3)}(μ-dppm)(CO)7 give {Tp∗(OC)2Mo}C(CC)2C{Co3(μ-dppm)(CO)7} (9) via a phosphine-gold(I) halide elimination reaction. The C3 complexes Tp′(OC)2MCCCRu(dppe)Cp∗ (Tp′ = Tp, M = Mo 10, W 11; Tp′ = Tp∗, M = Mo 12) were obtained from 2-4 and RuCl(dppe)Cp∗ via KF-induced metalla-desilylation reactions. Reactions between Mo(CBr)(CO)2Tp∗ and Ru{(CC)nAu(PPh3)}(dppe)Cp∗ (n = 2, 3) afforded {Tp∗(OC)2Mo}C(CC)n{Ru(dppe)Cp∗} (n = 2 13, 3 14), containing C5 and C7 chains, respectively. Single-crystal X-ray structure determinations of 1, 2, 7, 8, 9 and 12 are reported. 相似文献
6.
《Journal of organometallic chemistry》2005,690(6):1612-1619
Novel square-planar compounds [M(NC5H4CCH)2(dppp)](OTf)2 (M = Pd (1), Pt (2)), [Pt(CCC6H4CN)2(dppp)] (3) and [Pt(C6H4CCC5H4N)2(dppp)] (4) (dppp = 1,3-bis(diphenylphosphino)propane) were prepared and characterised. Their potential as building blocks in the generation of heterobimetallic squares was studied. The reaction of 4 and the ditopic acceptor species [Pd(H2O)2(dppf)](OTf)2 enabled a tetrametallic metallocycle containing two platinum and two palladium atoms to be obtained. The crystal X-ray structure of 4 shows that the Pt?N vectors are nearly perpendicular, and confirm the suitability of the compound to act as a corner unit for the construction of molecular squares. 相似文献
7.
H.J. Breunig T. Borrmann O. Moldovan R.P. Wagner 《Journal of organometallic chemistry》2009,694(3):427-91
Syntheses of [Me3SbM(CO)5] [M = Cr (1), W (2)], [Me3BiM(CO)5] [M = Cr (3), W (4)], cis-[(Me3Sb)2Mo(CO)4] (5), [tBu3BiFe(CO)4] (6), crystal structures of 1-6 and DFT studies of 1-4 are reported. 相似文献
8.
Xuan Xu Liang Fang Guo-Chun Yang Zhong-Min Su 《Journal of organometallic chemistry》2006,691(9):1927-1933
To study the Ru-M interactions and their effects on 31P NMR, complexes [Ru(CO)3(Ph2Ppy)2] (py = pyridine) (1) and [Ru(CO)3(Ph2Ppy)2MCl2] (M = Zn, 2; Cd, 3; Hg, 4) were calculated by density functional theory (DFT) PBE0 method. Moreover, the PBE0-GIAO method was employed to calculate the 31P chemical shifts in complexes. The calculated 31P chemical shifts in 1-3 follow 2 > 3 > 1 which are consistent to experimental results, proving that PBE0-GIAO method adopted in this study is reasonable. This method is employed to predict the 31P chemical shift in designed complex 4. Compared with 1, the 31P chemical shifts in 2-4 vary resulting from adjacent Ru-M interactions. The Ru → M or Ru ← M charge-transfer interactions in 2-4 are revealed by second-order perturbation theory. The strength order of Ru → M interactions is the same as that of the P-Ru → M delocalization with Zn > Cd > Hg, which coincides with the order of 31P NMR chemical shifts. The interaction of Ru → M, corresponding to the delocalization from 4d orbital of Ru to s valence orbital of M2+, results in the delocalization of P-Ru → M, which decreases the electron density of P nucleus and causes the downfield 31P chemical shifts. Except 2, the back-donation effect of Ru ← M, arising from the delocalization from s valence orbital of M2+ to the valence orbital of Ru, is against the P-Ru → M delocalization and results in the upfield 31P chemical shifts in 4. Meanwhile, the binding energies indicate that complex 4 is stable and can be synthesized experimentally. However, as complex [Ru(CO)3(Ph2Ppy)2HgCl]+5 is more stable than 4, the reaction of 1 with HgCl2 only gave 5 experimentally. 相似文献
9.
Ching-Shiang Fang 《Journal of organometallic chemistry》2009,694(3):404-1617
Mononuclear complexes of the type, M(CO)4[Se2P(OR)2] (M = Mn, R = iPr, 1a; Et, 1b; M = Re, R = iPr, 3a; Et, 3b) can be prepared from either [-Se(Se)P(OiPr)2]2 (A) or [Se{-Se(Se)P(OEt)2}2] (B) with M(CO)5Br. O,O′-dialkyl diselenophosphate ([(RO)2PSe2]-, abbreviated as dsep) ligands generated from A and B act as a chelating ligand in these complexes. Upon refluxing in acetonitrile, these mononuclear complexes yield dinuclear complexes with a general formula of [M2(CO)6{Se2P(OR)2}2] (M = Mn, R = iPr, 2a; Et, 2b; M = Re, R = iPr, 4a; Et, 4b). Dsep ligands display a triconnective, bimetallic bonding mode in the dinuclear compounds and this kind of connective pattern has never been identified in any phosphor-1,1-diselenoato metal complexes. Compounds 2b, 3b, and 4 are structurally characterized. Compounds 2b and 3b display weak, secondary Se?Se interactions in their lattices. 相似文献
10.
Marino Basato Giacomo Facchin Mirto Mozzon Paolo Sgarbossa Augusto Tassan 《Journal of organometallic chemistry》2004,689(2):454-462
2-(Azidomethyl)phenyl isocyanide, 2-(CH2N3)C6H4NC (AziNC), coordinates to some cationic Pt(II) and Pd(II) species to afford isocyanide complexes of the type trans-[MCl(AziNC)(PPh3)2][BF4] (M=Pt, l; Pd, 2). AziNC is coordinated also in some neutral Pt(II) and Pd(II) species such as [MCl2(AziNC)2] (M=Pt, 3; Pd, 4) derived from the reactions of 2 equiv. of AziNC with [PtCl2(COD)] and [PdCl2(MeCN)2], respectively. Complexes 1 and 2 react with 1 equiv. of PPh3 affording the heterocyclic carbene complexes trans-[MCl{(H)}(PPh3)2][BF4] (M=Pt, 5; Pd, 6). Complexes 3 and 4 react with 1 equiv. of PPh3 displacing the isocyanide with the formation of the complexes cis-[MCl2(AziNC)(PPh3)] (M=Pt, 7; Pd, 8). These latter ones react with 2 equiv. of PPh3 affording as the final products the cationic carbene species trans-[MCl{(H)}(PPh3)2][Cl] (M=Pt, 9; Pd, 10). Complex 5 was also characterized by single crystal X-ray diffraction. The carbene complex is square-planar and the angle formed between the platinum square plane and the heterocyclic carbene ligand is 87.9(2)°. The C(1)-N(1) and C(1)-N(2) bond distances in the latter of 1.32(2) and 1.30(2) Å, respectively, are short for a single bond and indicate extensive π-bonding between the nitrogen atoms and the carbene carbon. 相似文献