The reactions of [MI2(CO)3(NCMe)2] (M = Mo or W) with one equivalent of L (L = pyridine or substituted pyridines) to give [WI2(CO)3(NCMe)L] and [M(μ-I)I(CO)3L]2

The complexes [MI₂(CO)₃(NCMe)₂] (M = Mo or W) react with one equivalent of L in CH₂Cl₂ at room temperature to give initially the mononuclear seven-coordinate complexes [MI₂(CO)₃(NCMe)L] which have been isolated for M = W; L = 3Cl-py, 3Br-py, 4Cl-py and 4Br-py. These compounds dimerise to give the iodidebridged dimers [M(μ-I)I(CO)₃L]₂ by displacement of acetonitrile. When M = Mo; L = 3Cl-py, 3Br-py, 4Cl-py and 4Br-py, and when M = Mo and W; L = py, 2Me-py (for M = W only), 4Me-py, 3,5-Me₂-py, 2Cl-py and 2Br-py, only the dimeric complexes have been isolated. The ease of dimerisation of [MI₂(CO)₃(NCMe)L] is discussed in terms of the steric and electronic effects of the substituted pyridines.     

Spectroscopic properties of [M(CN)5py]n− complexes [M  Fe(II), Co(III); py = pyridine]

The IR, electronic and NMR spectra of K₂[Co(CN)₅py]·H₂O and Na₃[fe(CN)₅py]·3H₂O, as well as the Mössbauer spectrum of the latter complex, are reported and discussed. In particular it is argued that the wavenumbers and intensities of the i.r.-active CN stretching vibrations and the NMR chemical shifts of the m- and p-but not o-protons suggest greater metal to ligand back π-bonding in the Fe(II) complex than in the Co(III) complex.     

配合物[M(CO)3(PPh2py)2](M=Fe,Ru)异构体的理论研究

对PPh2py配合物[M(CO)3(PPh2py)2](M=Fe, Ru)的三种构型的异构体1-6进行了研究. 其中PPh2py以两个P原子与M配位形成HH构型1(Fe)和4(Ru), 以一个P和一个N原子与M配位形成HT构型2(Fe)和5(Ru), 以两个N原子与M配位形成HH’构型3(Fe)和6(Ru). 结果表明, (1) PPh2py中P原子对HOMO轨道的贡献最大, PPh2py作为电子给体时易以P原子与金属原子结合. (2)从分子能量和相互作用能数据表明, 配合物中HH构型最稳定, HH'构型最不稳定, 这与合成产物为HH构型的结果一致. (3) 键长和Wiberg键级均表明P—M键比N—M键结合力强. P、M原子间存在σ键, 而N、Fe原子间仅存在nN→n*M或nN→σ*M-P的电荷转移作用. (4) HH构型中M对HOMO的贡献最大, PPh2py向M的电荷转移最强, 使M的负电荷最大, 故HH构型最易作为电子给体以M原子与第二个金属配位形成双核配合物.     

Darstellung und reaktionen von diphosphen-komplexen RPPR[M(CO)5]3 (M = Cr,Mo, W)

Decacarbonyldimetallates Na₂M₂(CO)₁₀ (M = Cr, Mo, W) react with dihalophosphanes, (R)P(Cl)₂, to yield trinuclear diphosphene complexes of the form RPPR[M(CO)₅]₃. The by-products of these reactions are diphosphane- and phosphido-bridged complexes.The trinuclear diphosphene compounds add HX (X = CH₃COO, CH₃O) or dienes to the PP double bond; in the course of these additions one M(CO)₅ group is cleaved and binuclear derivatives of diphosphanes are obtained.     

RuH3[P(C6H5)3] 3 − as a ligand in complexes withM(CO)3 Fragments (M = Cr,Mo, W)

The reactions of RuH₃[P(C₆H₅)₃] ₃ ^– with Cr(CO)₃(CH₃CN)₃, Mo(CO)₃ (diglyme), or W(CO)₃(C₃H₂CN)₃ resulted in the formation of the appropriate [(H₅C₆)₃P]₃Ru(-H)₃ M(CO) ₃ ^– complexes, which have been characterized analytically, spectroscopically, and in one case (M = Cr) by an X-ray diffraction study of the K [N(C₂H₄OC₂H₄OCH₃)₃]⁺ salt. This complex crystallizes in the triclinic space group Pl witha = 13.666(6),b= 13.7901(7),c = 18.147(8) A,a = 93.23(3)°, = 94.07(4)° = 90.43(4)°, andV = 3405.6 A³ for Z = 2. Final discrepancy indices ofR = 0.048 and Rù = 0.056 were obtained. The hydride ligands, all of which could be located and their positional coordinates refined, completed local pseudo-octahedral coordination about both the ruthenium and thechromium centers. The Ru-H bonds are significantly shorter than the Cr-H ones, 1.65(4) vs. 1.92(4) A, and the Ru-Cr bond distance is 2.5474(9) A.     

Synthesis and Crystal Structure of [Ni(Ⅱ)(L)(py)3]·(py)

The title complex, C37H34N6NiO5, has been prepared and characterized by X-ray diffraction analysis. It crystallizes in the monoclinic system, space group P21/c with a = 1.15244(8), b = 1.69679(12), c = 1.78341(13) nm, β = 102.2320(10)°, V = 3.4082(4) nm3, Z = 4, Mr = 701.41, F(000) = 1464, Dc = 1.367 g/cm3 and μ(MoKα) = 0.622 mm-1. The structure was refined to R = 0.0459 and wR = 0.1199 for 5718 observed reflections. The intramolecular hydrogen bonds in the crystal structure play important roles in the title complex's thermostability.     

Ruthenium heterocyclic thiolate complexes: CpRu(L)(L′)SR, [L = L′ = PPh3, 1/2 dppm, 1/2 dppe; L = PPh3, L′ = CO]

The synthesis and characterization of several new ruthenium complexes containing heterocyclic thiolate ligands are described. CpRu(PPh₃)₂Cl reacts with thiolate anions to give CpRu(PPh₃)₂SR, (1) [R = 2-mercaptobenzimidazolyl (a), 2-mercaptobenzothiazolyl (b), and 2-mercaptobenzoxazolyl (c)] in good yields. The CpRu(PPh₃)-(CO)SR (2) complexes are obtained by treating (1) with CO gas in THF at room temperature. The one-pot reaction of CpRu(PPh₃)₂Cl, thiolate anions with chelate bisphosphine ligands (P–P), gave CpRu(P–P)SR where P–P = Ph₂PCH₂PPh₂ (dppm) (3); Ph₂PCH₂CH₂PPh₂ (dppe) (4).     

The formation of alkyne and alkynyl complexes by reaction of 1-alkynes with trans-[M(N2)2(PH2PCH2CH2PPh2)2] (M  Mo OR W) and with [Mo(Ph2PCH2PPh2)3]: X-ray structure of trans-[Mo(CCPh)2(PH2PCH2CH2PPh2)2]

Reaction of RCCH (R  Ph, CO₂Meor CO₂Et) with trans-[M(N₂)₂(dppe)₂] (M  Mo or W; dppe  Ph₂PCH₂CH₂PPh₂) or [Mo(dppm)₃] (dppm  Ph₂PCH₂PPh₂) gives the alkyne complexes [M(RCCH)₂(diphos)₂] (diphos  dppe, M  Mo, R = Ph; dihpos  dppm, M  Mo, R  Ph or CO₂Me) and the alkynyl complexes trans-[M(cCR)₂(dppe)₂], [MH₂(CCR)₂ (dppe)₂] (M  Mo or W. R  Ph, CO₂Me or CO₂Et) and cis-[WH(CCCO₂Me)(dppe)₂]: the X-ray structure of trans-[Mo(CCPh)₂(dppe)₂] is reported.     

Phosphine-centred resolution of (η4-diene)Fe(CO)3 complexes: (η4-tropone)Fe(CO)2L and (η4-isoprene)Fe(CO)2L [L = (+)-(neomenthyl)PPh2]

(η⁴-Tropone)Fe(CO)₃ and (η⁴-isoprene)Fe(CO)₃ form separable diastereoisomers on substitution of CO by (+)-(neomenthyl)PPh₂. In the tropone complex, diastereoisomer interconversion occurs by a 1,3-metal shift. The absolute configuration of the isoprene complex has been determined crystallographically.     

Synthesis,spectral properties and reactions of the novel dinuclear alkyne complexes [M(μ-I)I(CO)(NCMe)(η2-PhC2R)]2 (M = Mo or W,R = Ph or Me)

[MI₂(CO)₃(NCMe)₂] (M = Mo or W) and PhC₂R (R = Ph or Me) react in CH₂Cl₂ to initially afford the “four-electron” alkyne complexes [MI₂(CO)(NCMe)₂(η²-PhC₂R)], which subsequently dimerize to the novel iodide-bridged compounds [M(μ-I)I(CO)(NCMe)(η²-PhC₂R)]₂, with loss of acetonitrile. These complexes react via symmetrical cleavage of the iodide bridges.     

Synthesis and Crystal Structure of [Ni(II)(L)(py)_3]·(py)

1 INTRODUCTION Schiff bases and their metal complexes are useful reagents in organic synthesis[1], and they have exhi- bited some biological activities as anticancer and antitumor drugs[2]. The crystal structures and physi- cal and chemical properties of many Schiff bases and their transition metals complexes have been re- ported[3~5]. Further interest in the coordination che- mistry of nickel(II) arises from the role of these complexes in several catalytic reactions, such as electrocat…     

The oxidative addition of SnCl4 to [W(CO)4(NCMe)(PPh3)]. The X-ray crystal structure of [WH(CO)3(NCMe)(PPh3)2][SnCl5·MeOH]

The oxidative addition reaction of SnCl₄ with [W(CO)₄(NCMe)(PPh₃)] in acetonitrile gives a mixture of seven-coordinate tungsten(II) compounds: [WCl(SnCl₃)(CO)₃(NCMe)(PPh₃)] (1), [WCl₂(CO)₃(NCMe)(PPh₃)] (2), [WCl(SnCl₃)(CO)₂(NCMe)₂(PPh₃)] (3), and [WCl₂(CO)₂(NCMe)₂(PPh₃)] (4) identified by IR and NMR (¹H, ¹³C{¹H}, and ³¹P{¹H}) studies. Treatment of [W(CO)₄(NCMe)(PPh₃)] with 1 equiv. of SnCl₄ in CH₂Cl₂ solution besides compounds 1 and 2 also gives ionic species such as [HPPh₃]⁺ and [SnCl₆]²⁻ and cationic tungsten(II) complexes. The crystal structure of one of these, [WH(CO)₃(NCMe)(PPh₃)₂][SnCl₅·MeOH] (5), has been established by single-crystal X-ray diffraction. The IR, ¹H, ¹³C{¹H} and ³¹P{¹H} spectra of 5 are also described and can be correlated with the crystallographically observed geometry. A notable feature of 5 is the presence of an agostic interaction of the hydride ligand with one of the carbonyl ligands.     

Synthesis and characterisation of [AgL(μ-PR2)M(CO)5], L= 1,10-phenanthroline or tricyclohexylphosphine; M = Cr,Mo, W

The new heterobimetallic phosphide-bridged compounds [AgL(μ-PR₂)M(CO)₅], (L = 1,10-phenanthroline or tricyclohexylphosphine: M = Cr, M, W) have been prepared from AgO₃SCF₃, M(CO)₅PR₂H and the ligand L in the presence of Et₂NH or MeO⁻ as base, and characterized by ³¹P NMR spectroscopy.     

Cluster synthesis. 42. The synthesis and crystal and molecular structures of the sulfur-bridged platinum-ruthenium carbonyl cluster compounds PtRu3(CO)9 L(PPh3)(μ3-S)2 (L=CO,PPh3) and PtRu4(CO)12(PPh3)(μ4-S)2

Two new mixed metal cluster complexes PtRu₃(CO)₁₀(PPh₃)(₃-S)₂,3 14% yield and PtRu₃(CO)₉(PPh₃)₂(₃-S)₂,4 23% yield were obtained from the reaction of Ru₃(CO)₉(₃-S)₂,1 with Pt(PPh₃)₂(C₂H₄) at 0°C. The cluster of4 consists of a spiked triangle of four metal atoms with two triply bridging sulfido ligands. The reaction of Ru₄(CO)₁₁(₄-S)₂,2 with Pt(PPh₃)₂(C₂H₄) yielded the expanded mixed-metal cluster complex PtRu₄(CO)₁₂(PPh₃)(₄-S)₂,5 in 12% yield. The structure of the cluster5 can be described as a pentagonal bipyramid of five metal atoms and two sulfido ligands with one metal-metal bond missing. Compounds4 and5 were characterized by a single-crystal X-ray diffraction analyses.     

Octahedral cluster Mo complexes (Bz3NH)3[Mo6OCl13] and (Bz3NH)2[Mo6Cl14] · 2CH3CN: Synthesis, crystal structure and properties

The salts (Bz₃NH)₃[Mo₆OCl₁₃] (I) and (Bz₃NH)₂[Mo₆Cl1₄] · 2CH3CN (II) were obtained by reacting melted tribenzylamine with cluster Mo compounds. Compound II contains a known cluster anionic complex [Mo₆Cl₁₄]^2?. Compound I includes novel cluster anionic complex [Mo₆OCl₁₃]^3?, where one internal Cl atom is replaced by the O atom. Complex II exhibits phosphorescence in a long-wavelength region of visible spectrum.     

Correlation between solvatochromism and back-bonding in four isomeric (α-diimine)M(CO)4 complexes,M = Cr,Mo, W

Long-wavelength charge transfer absorption energies of isomeric complexes (bidiazine)M(CO)₄, (bidiazine = 3,3′-bipyridazine, 2,2′- and 4,4′-bipyrimidine, 2,2′-bipyrazine; M = Cr, Mo, W) were measured in various solvents and compared with those for corresponding 2,2′-bipyridine complexes. Linear correlations of energies of absorption maxima with solvent parameters E_MLCT revealed that the solvent dependence Δυ/gDE_MLCT within the bidiazine series increases with decreasing absolute charge transfer transition energy in a given solvent, i.e. with increasing back-donation into the ligand π orbital. Complexes of the most strongly back-bonding ligand, 4,4′-bipyrimidine, thus display by far the most pronounced solvent dependence, with Δυ/gdE_MLCT 4100 cm ⁻¹ for the molybdenum system.     

配合物[M（CO）3（PPh2py）2]（M=Fe，Ru）异构体的理论研究

对PPh2py配合物[M(CO)3(PPh2py)2](M=Fe,Ru)的三种构型的异构体1-6进行了研究.其中PPh2py以两个P原子与M配位形成HH构型1(Fe)和4(Ru),以一个P和一个N原子与M配位形成HT构型2(Fe)和5(Ru),以两个N原子与M配位形成HH'构型3(Fe)和6(Ru).结果表明,(1)PPh2py中P原子对HOMO轨道的贡献最大,PPh2py作为电子给体时易以P原子与金属原子结合.(2)从分子能量和相互作用能数据表明,配合物中HH构型最稳定,HH'构型最不稳定,这与合成产物为HH构型的结果一致.(3)键长和Wiberg键级均表明P-M键比N-M键结合力强.P、M原子间存在σ键,而N、Fe原子间仅存在nN→nM或nN→σM-P的电荷转移作用.(4)HH构型中M对HOMO的贡献最大,PPh2py向M的电荷转移最强,使M的负电荷最大,故HH构型最易作为电子给体以M原子与第二个金属配位形成双核配合物.     

About the Reaction of C(PPh3)2 with [M(CO)6] (M = Cr,Mo): Unusual Formation of μ-Carbonato Complexes of Mo under Participation of THF

Attempts to synthesize complexes of group 6 carbonyl compounds [M(CO)₆] (M = Cr, Mo, W) with the carbone C(PPh₃)₂ ( 1 ) via the photo chemically created adducts [(CO)₅M(THF)] lead to quantitative formation of the salts [HC(PPh₃)₂]₂[M₂(CO)₁₀] ( 2 , Cr; 3 , Mo; 4 , W). Alternatively, a long-time thermal reaction of [Mo(CO)₆] performed with 1 in THF generates a series of products initiated by a Wittig-type reaction. In addition to 3 , minor amounts of [(CO)₅MoCCPPh₃] ( 8 ), [(CO)₅MoO₂CC{PPh₃}₂] ( 5 ), and the carbonate complexes [HC(PPh₃)₂]₂[(CO)₅Mo(CO₃)Mo(CO)₄] ( 6 ) and [HC(PPh₃)₂]₂[(CO)₄Mo(CO₃)Mo(CO)₄] ( 7 ) were found. Compounds 2 , 3 , 5 , 6 , and 7 were characterized by X-ray analyses, ³¹P NMR, and IR spectroscopy. The water, necessary for the formation of the carbonate, stems from decomposition of THF.     

The first decaruthenium hydrido cluster: synthesis and crystal structure of [N(PPh3)2]2[Ru10C(CO)24]·C6H14 and [N(PPh3)2][HRu10C(CO)24]

X-ray structural studies of new thermolysis products from the reaction of Ru₃(CO)₁₂ in heptane in the presence of 1,3,5-trimethylbenzene (mesitylene) confirm that they are the decaruthenium carbido-cluster dianion [Ru₁₀C(CO)₂₄]²⁻ (I) and the hydrido decaruthenium carbido-cluster monoanion [HRu₁₀C(CO)₂₄]⁻ (II). Both anions have the giant tetrahedron Ru₁₀ metal framework, and the monohydride provides the first example of a hydrido ligand in a tetrahedral Ru₄ cavity.     

Synthesis,crystal structures and spectral properties of cobalt (Ⅱ) complexes:[ CoL (N_3) ] ·ClO_4 and CoL (N_3)_2 [L=tris ((3,5-dimethylpyrazol-1-yl) methyl) amine

Two monomeric cobalt(Ⅱ)complexes,[CoL(N3)] ClO4(1)and CoL(N3)2(2),where L is tris((3,5-dimethylpyrazol-1-yl)methyl)amine,were synthesized and their crystal structures were determined by X-ray diffraction technique.Complex 1 is five coordinated with one azide nitrogen atom and four nitrogen atoms of the tris((3,5-dimethylpyrazol-l-yl)-methyl)amine ligand,and the metal center is in distorted trigonal bipyramidal environment.Complex 2 is six coordinated distorted octahedron with the two azide nitrogen atoms and four nitrogen donors of the tris((3,5-dimethylpyrazol-1-yl)-methyl)amine ligand.The solution behaviors of the title complexes have been further investigated by UV-Vis,and 1H NMR analysis.It is found that the formation of 1 and 2 depends on the molar ratio of the azide ion to metal salt and ligand Complex 1 attached with one azide group is more stable and easy to generate than complex 2 incorporated with two azide groups,and the reasons were well discussed.