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1.
Unstable transition metal compounds formed from hydridosilacyclobutanes are described: 1-methyl-1-silacyclobutane reacts with nonacarbonyldiiron to give the complexes [Fe(CO)4(H){H2}] and [(H)Me}(CO)4], and with bis(triphenylphosphine)(ethylene)platinum(0) to give [Pt(H)(PPh3)2{H2}]. 相似文献
2.
Chelate complexes of the type (CO)4MiX2 (X = Me, Cl) have been prepared from Na[Mn(CO)5] and HMn (CO)5, respectively, by two-step reactions with the ligands Me2PCH2CH2SiX2R′ using alkali salt, amine or HCl elimination. (CO)4MiCl2 is also obtained by cleavage of Mn2(CO)10 with Me2PCH2CH2SiCl3. IN the case of HMn (CO)5 the intermediates (CO)4Mn (H) L [L = Me2PSiMe3, Me2PCH2CH2SiMe2 (NMe2), Me2PCH2CH2SiCl2 (NMe2] can be isolated. The new compounds were identified by analytical and spectroscopic (IR, PMR, MS) methods. 相似文献
3.
Silicon-transition metallic silacyclobutanes CpFe(L2)H2 [L = CO or Ph2MeP; or L2 = (CO)(Ph2MeP)] have been prepared and their reactions (substitution at Si or Fe, Si—Fe cleavage, or ring-opening) studied. 相似文献
4.
Georg Grötsch Wolfgang Malisch Herbert Blau 《Journal of organometallic chemistry》1983,252(2):C19-C22
The reaction of the phosphonium metallates Me4P[C5R5(CO)(Me3P))R′] (M = W, R = H, R′ = Et (1a); M = Mo, R = Me, R′ = Me (1b)) with the silylating reagent Me3SiOSO2CF3 yields the neutral complexes C5R5(CO)(Me3P))R (2a, 2b) bearing a chelating O(2), C(4)-trimethylsiloxybutenone ligand. The structure of the new compounds is established by the IR, 1H and 31P NMR spectra. 相似文献
5.
Ronald L. Bennett Michael I. Bruce F.Gordon A. Stone 《Journal of organometallic chemistry》1975,94(1):65-74
The interaction of azobenzene and MnR(CO)5 (R Me, Et, CH2Ph, CH2-C6Me5, COCF3, COCH2C6F5, COCH2OPh, Ph or C6F5) affords MPh)-(CO)4, together with a binuclear complex Mn2(CO)6(C12H10N2) in some cases. The metallation reaction is shown to proceed most readily with Mn-(CH2Ph)(CO)5; with this reagent, the metallated complexes MMe2)-(CO)3[PMe2(CH2Ph)] (two isomers) and MsMe2(CO)4 have been obtained on treatment with EMe2(CH2Ph) (E P and As, respectively). 相似文献
6.
G.R. Clark C.M. Cochrane W.R. Roper L.J. Wright 《Journal of organometallic chemistry》1980,199(2):C35-C38
The osmium carbyne complex, Os(CR)Cl(CO)(PPh3)2, (R p-tolyl) reacts with Group I halides to form the mixed dimetallocyclopropene species, R)Cl(CO)(PPh3)2, R)Cl(CO)(PPh3)2, R)Cl(CO)(PPh3)2, and [R)Cl(CO)(MeCN)(PPh3)2] ClO4 X-ray crystal structure determination of R)Cl(CO)(PPh3)2 confirms the presence of a three-membered ring and the structure can be viewed as the “acetylene-like” interaction of an osmium—carbon triple bond with AgCl. In acid solution AgCl is precipitated and an alkylidene complex results from proton addition to the carbyne ligand. 相似文献
7.
Martin A. Bennett Tai-Nang Huang Jozef L. Latten 《Journal of organometallic chemistry》1984,272(2):189-205
The η-hexamethylbenzenehydridoruthenium(II) complexes RuHCl(η-C6Me6)L (L = PPh3 (11), AsPh3 (12), P(C6H4-p-F)3 (14), P(C6H4-p-Me)3 (15), P(C6H4-p-OMe)3 (16), P-t-BuPh2 (17), P-i-PrPh2 (18), P-i-Pr3 (19), PCy3 (20) and P-t-BuMe2 (21)) have been made by heating [RuCl2(η-C6Me6)]2, the ligand and sodium carbonate in propan-2-ol. The triarylphosphine complexes 11, 14 and 15 react with methyllithium to give aryl ortho-metallated hydridoruthenium(II) complexes such as Ph2)(η-C6Me6) (22) and 19 similarly gives the isopropyl cyclometallated complex -i-Pr2(η-C6Me6) (29) as a mixture of diastereomers. Reaction of 17 with methyllithium gives initially the t-butyl cyclometallated complex Ph2)(η-C6Me6) (25) which isomerizes by a first order process (k.2 h?1 in C6D6 or THF-d8 at 50°C) to the aryl ortho-metallated complex -t-BuPh)(η-C6Me6) (26). The similarly generated isopropyl cyclometallated complex Ph2)(η-C6Me6) (27) has not been isolated in a pure state owing to rapid isomerization to -i-PrPh)(η-C6Me6) (28); both 27 and 28 exist as a pair of diastereomers. The formation of the cyclometallated complexes and the isomerizations are thought to involve intermediate 16-electron ruthenium(O) complexes Ru(η-C6Me6)L. 相似文献
8.
Hans-Peter Abicht Peter Lehniger Kurt Issleib 《Journal of organometallic chemistry》1983,250(1):609-616
The complexes of type R2)2 (M = Pd, Pt) are readily deprotonated by n-Buli under various conditions yielding μ-C-bis-dilithiated species. The resulting carbanions are attacked by the electrophiles Mel, Me3SiCl and Ph2PCl to form the corresponding disubstituted derivatives. The reaction with AuCl . PPh3 yields heterobimetallic complexes with two different MC σ-bonds. The compounds obtained are analytically and spectroscopically characterized. 相似文献
9.
Augusto De Renzi Achille Panunzi Michaelangelo Scalone Aldo Vitagliano 《Journal of organometallic chemistry》1980,192(1):129-132
Amination of PtII-allene complexes of the type cis[PtCl2(Me2CCCHR)(PPh3)] gives the new four-membered C, N chelate aminoalkenyl complexes [Me2(PPh3)Cl]. These undergo ready insertion of carbon monoxide into the CPt σ-bond; the resulting acyl complexes are oxidized by hydrogen peroxide to aminoacidato complexes, and the free unsaturated β-aminoacids can be recovered in good yield by ligand displacement. 相似文献
10.
David A. Clarke Martin M. Hunt Raymond D.W. Kemmitt 《Journal of organometallic chemistry》1979,175(2):303-313
Reactions of alloxan (all) with [PtL(PPh3)2] (L′= -stilbene, L″ diphenylacetylene) afford the side-bonded ketone complex [Pt(all)(PPh3)2] which may also be obtained from the hydrate of alloxan and [PtL′(Pph3)2]. Similarly diethyl oxomalonate (dio) and [Pt(PPh3)4] afford a side-bonded ketone complex [Pt(dio)(PPh3)2]. Reaction of isatin with [Pt(PPh34] gives -[PtH{}(PPh3)2] and benzoyl cyanide and [PtL′(PPh3)2] give -[Pt(CN)(COPh3)2] and -[Pt(CN)2(PPh2)2]. 相似文献
11.
Duncan C.L. Perkins Richard J. Puddephatt Charles F.H. Tipper 《Journal of organometallic chemistry》1980,191(2):481-488
The products of the photolysis of a number of platinacyclopentanes in solution at 25°C under a variety of conditions have been determined. With [I2PH2(L2)] (L = PMe2Ph, PPh3) in CH2Cl2, CH2Br2 and (CH3)2SO the hydrocarbon products are exclusively ethylene and but-1-ene. Formation of the latter through a 1,3-hydrogen shift is preceded by phosphine ligand dissociation. The photolysis of [ICH3PH2(L2)] gave methane, ethylene, but-1-ene and n-pentane together with a little n-butane, the methane being formed from internal hydrogen abstraction by the CH3 group in the excited reactant molecule. Photodecomposition of the platinum(II) compounds [PH2(L2)] (L = (PMe2Ph)2, (PPh3)2, Ph2PCH2CH2PPh2) gave ethylene, but-1-ene, pent-1-ene (with the halogenated solvents) and with some systems appreciable yields of n-butane, the latter being the results of internal abstraction of two hydrogen atoms by the C4H8 moiety. The formation of pentene is probably preceeded by the addition of CH2Cl2 or CH2Br2 to the excited reactant molecule. Addition of diphenylphosphine promotes the production of n-butane. 相似文献
12.
《Polyhedron》2001,20(9-10):1089-1095
13.
The chelating ligand Me3COSiMe2N(CMe3)H (III) can easily be prepared in high yields and has been employed for the synthesis of some metal derivatives. With n-butyllithium III forms [Me2Si(Me3CO)(Me3CNLi)]2 (IV), which is found to be dimeric in solution and in the gas phase. When IV is allowed to react with thallium(I) chloride in diethyl ether the monomeric, highly reactive Me2Si- (Me3C) (II) is formed under precipitation of lithium chloride. The cyclic structure and the physical properties of II can be understood on the basis of isosteric relation to cyclic diazasilastannylenes. II forms the tetramer (TlOMe)4 with methanol and does not add methyl iodide to the metal, the thalium containing product being TII. With magnesium dichloride in diethyl ether yields thallium(I) chloride and the spiro compound [Me2Si(Me3CO)(Me3CN)]2-Mg (VI), in which magnesium exhibits 4-fold coordination. 相似文献
14.
Os(η2-CH2O)(CO)2(PPh3)2 reacts with CSe2 to form a metallacycle O]Se)(CO)2(PPh3)2. This compound breaks down to Os(η2-CH2Se)(CO)2(PPh3)2 with probable loss of COSe. An alternative route to Os(η2-CH2Se)(CO)2(PPh3)2 and also Os(η2-CH2Te)(CO)2(PPh3)2 is through reaction of Os(CH2I)I(CO)2(PPh3)2 with SeH? and TeH?, respectively. HCl with Os(η2-CH2E)(CO)2(PPh3)2 (E = Se or Te) gives OsCl(EMe)(CO)2(PPh3)2 while methyl iodide gives [Os(η2-CH2EMe)(CO)2 - (PPh3)2] I. BH4? reacts with these cations to cleave the CE bond and form Os(CH3)(EMe)(CO)2(PPh3)2. 相似文献
15.
Sulfinyl fluoride and N-(F-isoprophyl)iminosulfur difluoride form the compounds, O(CH3) and i-C3F7N(CH3 with symdimethylethylenediamine (1). In contrast, CF3C(O)NSF2 and (Rf)2SF2 (Rf = CF3, i-C3F7 form only acyclic compounds, CF3C(O)N(CH3)CH2CH2N(CH3)C(O)CF3 and RfSN(CH3)CH2CH2N(CH3)SRf with (1). With PF3, PF5 and OPF3, cyclic compounds F, F3, and -(O)F result. When the latter two compounds are reacted further with LiNC(CF3)2, N(CH3)CH2CH2N(CH3)PF2NC(CF3)2 and (O)NC(CF3)2) form. 相似文献
16.
C5H5FeC5H4CH2NMe2 reacts with sodium chloropalladate(II) in the presence of sodium acetate to give the internally metallated binuclear species [Me2}2] (X = Cl). The corresponding iodide was prepared as were mononuclear species [Me2}] and [Me2}L] L = PMe2Ph, AsMe2Ph, P(OMe)3 or PPh3. 1H NMR data are given. 相似文献
17.
The complexes [IrH(CO)(PPh3)3], trans-[IrCI(CO)- (PPh3)2], [RhH(PPh3)4], [Pd(PPh3)4], [Pt(trans-stilbene)(PPh3)2] and [Pt(η3-CH2-COCH2)-(PPh3)2] catalyse the rearrangement of Me3SiCH2C(O)CH2Cl to CH2?C(OSiMe3)-CH2Cl. 相似文献
18.
19.
Ekkehard Lindner Faouzi Bouachir Riad Fawzi Dieter Hubner 《Journal of organometallic chemistry》1982,235(3):345-352
The platinacyclopentane derivative [Cl(CH2)3R2P](Cl) is formed by action of Cl(CH2)3PR2 on Pt(COD)2 in n-hexane via the not isolable Pt[PR2(CH2)3Cl]2 (R C6H11) by oxidative addition of a CCl bond to platinum. [μ-CIRh(CO)2]2 reacts in benzene with Cl(CH2)3PR2 under partially CO substitution to give the stable intermediate Cl(OC)Rh[PR2(CH2)3Cl]2. In boiling toluene oxidative addition of a CCl bond to rhodium occurs under formation of the phospharhodacyclopentane [CI(CH2)3R2P] Cl2(OC)- (R C6H5). The 31P{1H}-NMR spectra of the rhodium compound is characterized by an ABX system, that of the platinum by superposition of an ABX pattern with an AB spectrum. 相似文献
20.
Treatment of Ir2Cl2(C8H14)4 with the phosphines t-Bu3?nP(CH2CMe3)n (n = 3,2,1) in hot toluene followed by crystallization of the products from C7H8/ EtOH mixtures gave the cyclometallated hydrides (C8H14)2Ir-μ-Cl2(CH2CMe3)2][P(CH2 (I) [t-BuP(CH2CMe3)2]2H2Ir-μ-Cl2But(CH2CMe3)][t-BuP(CH2CMe3)2] (II), and [(t-Bu2rCl]2 (III). The dihydrides IrH2Cl[t-BuP(CH2CMe3)2]2 (IIa) and IrH2Cl(t-Bu2PCH2CMe3)2 (IIIa) were also isolated; these species were, however, more conveniently obtained by bubbling hydrogen through the solution of Ir2Cl2 (C8H14)4 and the respective phosphine in toluene. i-Pr3 reacted with the olefiniridium(I) precursor in C7H8/EtOH to yield the carbonyl complexes (i-Pr3P)2H2Ir-μ-Cl2Ir(CO)(PPri3)2 (IV) and IrCl(CO)(PPi3)2 (IVa), no cyclometallated product being detected. The stereochemistries of the complexes were deduced from IR, 1H, 31P, and 13C NMR data. The crystal structures of IIIa and IVa were also determined. 相似文献