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1.
L. Summer Maffett Kelly L. Gunter Kevin A. Kreisel Glenn P.A. Yap Daniel Rabinovich 《Polyhedron》2007
The diamagnetic nickel mononitrosyl complexes (TmR)Ni(NO) (R = But, p-Tol) and (BmR)Ni(PPh3)(NO) (R = Me, But) have been readily prepared from Ni(PPh3)2(NO)Br and the appropriate Na(TmR) or Na(BmR) reagents, respectively. These species constitute the first nickel nitrosyl complexes supported by these ligand systems. An X-ray diffraction study of (Tmp-Tol)Ni(NO) confirmed its pseudo-tetrahedral geometry and the presence of a nearly linear nitrosyl ligand. In contrast, (BmMe)Ni(PPh3)(NO) can be best described as having a trigonal pyramidal geometry, a spatial arrangement unprecedented in nickel nitrosyl chemistry, which is facilitated by the disposition of the BmMe ligand and the presence of a weak intramolecular Ni?H–B interaction opposite to the apical triphenylphosphine ligand. 相似文献
2.
The reaction of [Ni(COD)2] with one equivalent of DABMes (DABMes = (2,4,6‐Me3C6H2)N=C(Me)‐C(Me)=N(2,4,6‐Me3C6H2)) affords a mixture of the compound [Ni(DABMes)2] ( 2 ) and starting material [Ni(COD)2]. The crystallographically characterized, diamagnetic complex 2 can be obtained in a stoichiometric reaction of [Ni(COD)2] and two equivalents of DABMes. This reaction can be accelerated by addition of 1‐chloro‐fluorobenzene or methyl iodide. In the presence of 1‐chloro‐fluorobenzene, [Ni(DABMes)(COD)] ( 3 ) is available via reaction of [Ni(COD)2] and one equivalent of DABMes. The crystallographically characterized complex 3 reacts with diphenylacetylene to afford [Ni(DABMes)(Ph‐C≡C‐Ph)] ( 4 ). A long‐wavelength absorption band in the UV‐Vis spectrum of this compound has to be assigned to a mixed MLCT/LL′CT transition, as quantum chemical calculations reveal. 相似文献
3.
《Journal of organometallic chemistry》1986,315(1):105-112
Neutral hydrido complexes [ML]ClH(PPh3)3 ([ML] = Ru(CO), Os(CO) and Ir(Cl)] react with thionitrosodimethylamine, Me2NNS, to give [ML]ClH-(SNNMe2)(PPh3)2 with H trans to Me2NNS, while the hydrido cations cis,trans-[[ML]H(SNNMe2)2(PPh3)2]+ are obtained from Me2NNS and [Ru(NCMe)2(CO)-(PPh3)2]+, [OsH(OH2)(CO)(PPh3)3]+ and [IrClH(NCMe)2(PPh3)2]+, respectively. The coordinatively unsaturated aryl complexes [ML′]Cl(p-tolyl)(PPh3)2 ([ML′]Ru(CO), Os(CO) and Os(CS)) coordinate one molecule of Me2NNS to give [ML′]Cl(p-tolyl)(SNNMe2)(PPh3)2, the chloride ligands of which are labile. Spectroscopic data suggest that in all these complexes the Me2NNS ligand adopts a η1(S) coordination mode. 相似文献
4.
《Journal of Coordination Chemistry》2012,65(5):417-425
In line with our investigations of rhenium nitrosyl complexes, we have studied the reaction of [ReCl3(NO)(OPPh3)(PPh3)] with pyridine. The [ReCl2(NO)(py)3] complex obtained in this reaction has been characterised by IR, electronic spectra and magnetochemical measurements; ligand field parameters and the electronic structure have been determined. The crystal and molecular structure of [ReCl2(NO)(py)3] has been solved by the heavy atom method. Crystals of [ReCl2(NO)(py)3] contain distorted octahedral molecules with the pyridine ligands in the mer-arrangement. The nitrosyl group is coordinated linearly to the rhenium atom as NO+. 相似文献
5.
Linear nickel nitrosyl compounds supported by tridentate nitrogen and selenium ligands, namely the tris(3,5-dimethylpyrazolyl)hydroborato and tris(2-seleno-1-mesitylimidazolyl)hydroborato complexes, [TpMe2]NiNO and [TseMes]NiNO, have been synthesized and structurally characterized by X-ray diffraction. Computational studies demonstrate that the linear nitrosyl ligand behaves as a trivalent X3 ligand such that the Ni-N interaction has multiple bond character. 相似文献
6.
New silver complexes of general formula [Ag(O3SCF3)(PPh2{bzt})n] (n = 1–3, bzt = benzo[1,2-b;4,3-b′]dithiophene) have been synthesized and characterized. Spectroscopic studies shown neutral ligand fluxionallity, typical of silver(I) complexes. The solid state structure of the complexes was determined by X-ray crystallographic studies, showing a decrease in structure complexity with increasing number of neutral ligands in silver coordination sphere: [Ag(O3SCF3)(PPh2{bzt})] is a dimer with two bridging triflate anions, further linked into polymeric bidimensional chains along bc plane, through Ag?Ph close contacts; Ag(O3SCF3)(PPh2{bzt})2] is also a dimmer with two bridging triflate anions, displaying an interesting packing feature, with zig-zag alignment of bzt groups along direction b; [Ag(O3SCF3)(PPh2{bzt})3] is a monomer. 相似文献
7.
N. Srinivasan V. Sathyaselvabala K. Kuppulekshmy P. Valarmathi S. Thirumaran 《Monatshefte für Chemie / Chemical Monthly》2009,40(6):1431-1436
Abstract
[Ni(4-mpipdtc)2] and [Ni(4-mpipdtc)(PPh3)(NCS)] (4-mpipdtc = 4-methylpiperidinecarbodithioate anion) have been characterized by electronic, IR, and NMR spectroscopy, single crystal X-ray analysis, and cyclic voltammetry. IR spectra of the complexes show the contribution of the thioureide form to the structures. 1H NMR spectra show the deshielding of α-CH2 protons on complexation. 13C NMR spectra shows interesting differences between the N13CS2 carbon signals of the parent complex [Ni(4-mpipdtc)2] and the mixed ligand complex [Ni(4-mpipdtc)(PPh3)(NCS)]. The N13CS2 carbon signal for [Ni(4-mpipdtc)(PPh3)(NCS)] is observed at 204.85 ppm with an upfield shift of about 3.8 ppm compared with that found in [Ni(4-mpipdtc)2] (201.06 ppm). The observed shielding in [Ni(4-mpipdtc)(PPh3)(NCS)] indicates the effect of PPh3 on the mesomeric drift of electron density toward nickel through the thioureide C–N bond. Single crystal X-ray analysis of [Ni(4-mpipdtc)2] and [Ni(4-mpipdtc)(PPh3)(NCS)] confirms the presence of four-coordinated nickel in a distorted square-planar arrangement with the NiS4 and NiS2PN chromophores, respectively. The C–N (thioureide) bond lengths of [Ni(4-mpipdtc)(PPh3)(NCS)] are shorter than those found in [Ni(4-mpipdtc)2], because of the presence of the π-acid (triphenylphosphine) in [Ni(4-mpipdtc)(PPh3)(NCS)]. Significant asymmetry in Ni–S bond distances was observed in Ni(4-mpipdtc)(PPh3)(NCS)] (2.162(2) and 2.211(2) ?). This observation clearly supports the less effective trans effect of SCN– over PPh3. The piperidine ring in the dithiocarbamate fragment is in the normal chair conformation. 相似文献8.
Perfluorocarboxylic acids (RFCOOH) (RF = CF3,C2F5 and (for Rh) C6F5) react with the species [M(NO)2(PPh3)2] (M = Ru, Os) and [M′(NO)(PPh3)3] (M′ = Rh, Ir) to yield new nitrosyl complexes [Ru(OCORF)3(NO)(PPh3)2], [OsH(OCORF)2(NO)(PPh3)2], [Os(OCORF)(NO)2(PPh3)2][OCORF], [Ir(OCORF)(NO)(PPh3)2][OCORF] and [Rh(OCORF)2(NO)(PPh3)2]. 相似文献
9.
Oliver J. Cooper Dr. David P. Mills Dr. Jonathan McMaster Dr. Floriana Tuna Prof. Eric. J. L. McInnes Dr. William Lewis Prof. Alexander J. Blake Dr. Stephen T. Liddle 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(22):7071-7083
Treatment of [K(BIPMMesH)] (BIPMMes={C(PPh2NMes)2}2?; Mes=C6H2‐2,4,6‐Me3) with [UCl4(thf)3] (1 equiv) afforded [U(BIPMMesH)(Cl)3(thf)] ( 1 ), which generated [U(BIPMMes)(Cl)2(thf)2] ( 2 ), following treatment with benzyl potassium. Attempts to oxidise 2 resulted in intractable mixtures, ligand scrambling to give [U(BIPMMes)2] or the formation of [U(BIPMMesH)(O)2(Cl)(thf)] ( 3 ). The complex [U(BIPMDipp)(μ‐Cl)4(Li)2(OEt2)(tmeda)] ( 4 ) (BIPMDipp={C(PPh2NDipp)2}2?; Dipp=C6H3‐2,6‐iPr2; tmeda=N,N,N′,N′‐tetramethylethylenediamine) was prepared from [Li2(BIPMDipp)(tmeda)] and [UCl4(thf)3] and, following reflux in toluene, could be isolated as [U(BIPMDipp)(Cl)2(thf)2] ( 5 ). Treatment of 4 with iodine (0.5 equiv) afforded [U(BIPMDipp)(Cl)2(μ‐Cl)2(Li)(thf)2] ( 6 ). Complex 6 resists oxidation, and treating 4 or 5 with N‐oxides gives [{U(BIPMDippH)(O)2‐ (μ‐Cl)2Li(tmeda)] ( 7 ) and [{U(BIPMDippH)(O)2(μ‐Cl)}2] ( 8 ). Treatment of 4 with tBuOLi (3 equiv) and I2 (1 equiv) gives [U(BIPMDipp)(OtBu)3(I)] ( 9 ), which represents an exceptionally rare example of a crystallographically authenticated uranium(VI)–carbon σ bond. Although 9 appears sterically saturated, it decomposes over time to give [U(BIPMDipp)(OtBu)3]. Complex 4 reacts with PhCOtBu and Ph2CO to form [U(BIPMDipp)(μ‐Cl)4(Li)2(tmeda)(OCPhtBu)] ( 10 ) and [U(BIPMDipp)(Cl)(μ‐Cl)2(Li)(tmeda)(OCPh2)] ( 11 ). In contrast, complex 5 does not react with PhCOtBu and Ph2CO, which we attribute to steric blocking. However, complexes 5 and 6 react with PhCHO to afford (DippNPPh2)2C?C(H)Ph ( 12 ). Complex 9 does not react with PhCOtBu, Ph2CO or PhCHO; this is attributed to steric blocking. Theoretical calculations have enabled a qualitative bracketing of the extent of covalency in early‐metal carbenes as a function of metal, oxidation state and the number of phosphanyl substituents, revealing modest covalent contributions to U?C double bonds. 相似文献
10.
Summary [OsCl(NO)2(PPh3)2]BF4 has been synthesised from [OsCl(CO)(NO)(PPh3)2] and NOBF4 and characterised in the solid state by a single crystal x-ray analysis determination and in solution by31P{1H} and15N n.m.r. studies. The nitrosyl ligands in [OsCl(NO)2(PPh3)2]+ are approximately linear,
and 170(1)0, and the co-ordination geometry about the metal ion is close to trigonal bipyramidal. This contrasts with the occurrence of a linear and a bent nitrosyl ligand in [RuCl(NO)2(PPh3)2]+ and a square-pyramidal metal geometry. In solution the15N n.m.r. spectrum of a 50%15N enriched sample of [OsCl(NO)2(PPh3)2]+ shows an equilibrium isotope effect similar to that reported for [RuCl(NO)2(PPh3)2]+ and suggests that both complexes exist in solution as rapidly equilibrating isomeric forms. 相似文献
11.
Mingos D. Michael P. Sherman Darren J. Williams Ian D. 《Transition Metal Chemistry》1987,12(6):493-496
Summary [RuCl(NO)2(dppbp)]BF4 (dppbp=(Ph2PCH2)2–) has been synthesised from [RuCl(NO)2(PPh3)2]BF4 and dppbp and characterised in the solid state by a single crystal x-ray determination. The [RuCl(NO)2(dppbp)]+ cation, has an approximately square-pyramidal co-ordination geometry with the dppbp ligand occupyingtrans-basal sites. The nitrosyl ligand in the apical site is partially bent [Ru–N–O=156.2(7)0] and the nitrosyl ligand in the basal side is essentially linear [Ru–N–O=172.5(6)0]. The1Hn.m.r. spectrum of [RuCl(NO)2(dppbp)]BF4 in solution has provided some insight into the dynamics of the complex in solution. 相似文献
12.
The phosphorus ylids Ph3PCHR (R = Me, Et, Prn, Pri, Bun, Cl, and OMe), and the ylids Ph3AsCH2, Me2SCH2, and Me2S(O)CH2 react with [Ni(η5-C5H5)Br(PPh3)] at room temperature to give the complexes [Ni(Ph3PCHR)(η5-C5H5(PPh3)] Br, [Ni(Ph3AsCH2)(η5-C5H5)(PPh3)]Br, [Ni(Me2SCH2)(η5-C5H5)(PPh3)]Br and [Ni{Me2S(O)CH2} (η5-C5H5)(PPh3)]Br, respectively. These are readily converted into the corresponding hexafluorophosphate salts on reaction with ammonium hexafluorophosphate. Under more forcing conditions the stabilised ylid Ph3PCHCOPh gives a product believed to be the complex [Ni(Ph3PCHCOPh)2(η5-C5H5)]Br, isolated and characterised as its PF6? salt. 相似文献
13.
《Journal of organometallic chemistry》1994,476(1):C9-C11
Treatment of a THF solution of trans-[ReCl(N2)(dppe)2] (dppe = Ph2PCH2CH2PPh2) with NO, in the presence of Tl[BF4], forms trans-[Re(NO)2(dppe)2][BF4], a rare formal 20-electron d8-rhenium nitrosyl complex which, by reaction with HX (X = BF4, Cl or HSO4), gives trans-[ReF(NO)(dppe)2][BF4] (2) (the X-ray structure of which is reported) or trans-[ReX(NO)(dppe)2]X (3, X = Cl or HSO4), respectively, as well as nitrous oxide. 相似文献
14.
M. Esther García Miguel A. Ruiz Luciano Marchiò 《Journal of organometallic chemistry》2011,696(2):559-567
The title dimanganese complexes react with NO (5% in N2) at room temperature to give as major products the corresponding hexanitrosyl derivatives [Mn2(NO)6(μ-L2)] in moderate yields, and they react rapidly with NO2 to give the corresponding hydride derivatives [Mn2(μ-H)(μ-NO2)(CO)6(μ-L2)], these having a nitrite ligand bridging the dimetal centre through the N and O atoms. The dppm-bridged dihydride also reacts selectively at 273 K with (PPN)NO2 to give first the nitro derivative (PPN)[Mn2(μ-H)(H)(NO2)(CO)6(μ-dppm)], which then transforms into the nitrosyl complex (PPN)[Mn2(μ-CO)(CO)5(NO)(μ-dppm)] at room temperature or above (dppm = Ph2PCH2PPh2; PPN+ = [N(PPh3)2]+). The latter anion reacts with (NH4)PF6 to give the hydride-bridged nitrosyl complex [Mn2(μ-H)(μ-NO)(CO)6(μ-dppm)] and with [AuCl(PPh3)] to give the trinuclear cluster [AuMn2(μ-NO)(CO)6(μ-dppm)(PPh3)] (Mn-Au = ca. 2.68 Å; Mn-Mn = 2.879(2) Å). Both products are derived from the addition of the added electrophile at the intermetallic bond and rearrangement of the nitrosyl ligand into a bridging position. In contrast, methylation of the anion with CF3SO3Me takes place at the nitrosyl ligand to yield the unstable methoxylimide derivative [Mn2(μ-NOMe)(CO)6(μ-dppm)]. Analogous reactions at the nitrosyl ligand take place upon the addition of HBF4·OEt2 to the nitrosyl-bridged hydrides [Mn2(μ-H)(μ-NO)(CO)n(μ-dppm)m] (n = 6, m = 1; n = 4, m = 2) to give the corresponding hydroxylimide derivatives [Mn2(μ-H)(μ-NOH)(CO)n(μ-dppm)m]BF4, which were also thermally unstable and could not be isolated nor fully characterized. 相似文献
15.
《Journal of organometallic chemistry》1988,354(3):C33-C36
Reaction of (η5-C5Me5)Re(NO)(PPh3)(CH3) and HBF4 · OEt2 in CH2Cl2 at −78°C gives the dichloromethane complex [η5-C5Me5Re(NO)(PPh3)(ClCH2Cl)]+ BF4−, which undergoes the title transformation at −35°C. The ReClCH2Cl carbon is attacked by halide nucleophiles (X−) to give XCH2Cl and the chloride complex (η5-C5Me5)Re(NO)(PPh3)(Cl), and exhibits a 13C NMR resonance that is coupled to phosphorus (d, 3J(CP) 5.0 Hz) and geminal hydrogens (t, 1J(CH) 186 Hz). 相似文献
16.
Mono- and Binuclear Dinitrosyl Complexes of Molybdenum and Tungsten. Crystal Structures of (PPh3Me)2[WCl4(NO)2], (PPh3Me)2[MoCl3(NO)2]2, and (PPh3Me)2[WCl3(NO)2]2 The complexes (PPh3Me)2[MCl4(NO)2] (M = Mo, W), and (PPh3Me)2[MCl3(NO)2]2, respectively, are prepared by reactions of the polymeric compounds MCl2(NO)2 with triphenylmethylphosphonium chloride in CH2Cl2, forming green crystals. According to the IR spectra the nitrosyl groups are in cis-position in all cases. The tungsten compounds as well as (PPh3Me)2[MoCl3(NO)2]2 were characterized by structure determinations with X-ray methods. (PPh3Me)2[WCl4(NO)2]: space group C2/c, Z = 4. a = 1874, b = 1046, c = 2263 pm, β = 119.99°. Structure determination with 3492 independent reflexions, R = 0.057. The compound consists of PPh3Me⊕ ions, and anions [WCl4(NO)2]2? with the nitrosyl groups in cis-position (symmetry C2v). (PPh3Me)2[WCl3(NO)2]2: Space group C2/c, Z = 4. Structure determination with 2947 independent reflexions, R = 0.059. (PPH3Me)2[MoCl3(NO)2]2: Space group P1 , Z = 1. a = 989, b = 1134, c = 1186 pm; α = 63.25°, β = 80.69°, γ = 69.94°. Structure determination with 3326 independent reflexions, R = 0.046. The compounds consist of PPh3Me⊕ ions, and centrosymmetric anions [MCl3(NO)2]22?, in which the metal atoms are associated via MCl2M bridges of slightly different lengths. One of the NO groups is in an axial position, the other one in equatorial position (symmetry C2h). 相似文献
17.
G. La Monica P. Sandrini F. Zingales S. Cenini 《Journal of organometallic chemistry》1973,50(1):287-296
Compounds of formula [M(NO)(PPh3)(N4R2)] (I) (M Rh, Ir; R SO2? C6H4CH3) have been obtained by the interaction of M(NO)(PPh3)3 with p-toluene-sulphonyl azide in benzene. These new compounds are formulated as tetrazene derivatives on the basis of chemical and spectroscopic data. They react with ligands, L, (e.g. CO, PPh3 to give pentacoordinated species of formula [M(NO)(PPh3(L)(N4R2)].The tetrazene derivatives yield the new nitrosyl compounds, M(NO)(PPh3)Cl2 (II) on treatment with HCl, the nitrogen-containing residue being converted into RN3 and RNH2 species. The compounds (II) are coordinatively unsaturated, and react with ligands L in the same manner as compounds (I), giving new derivatives of formula M(NO)(PPh3)(L)Cl2.IR and NMR spectra of the new compounds are reported and discussed. The presence in solution of a structure in which the chelate tetrazene ring has opened {e.g. [M(NO)(PPh3)(NR)(N3R)]} is suggested by NMR studies. 相似文献
18.
《Polyhedron》1987,6(6):1503-1507
The pentacoordinate rhodium nitrosyl complexes [RhBr2(NO)L2 [L = P(OPh)2Ph, P(OMe)Ph2 or P(OPri)Ph2] have been synthesized and the structures of [RhBr2(NO){P(OMe)Ph2}2] and [RhBr2(NO){P(OPri)Ph2}2] have been determined X-ray crystallographically. Both of these latter compounds are tetragonal pyramidal with the nitrosyl group apical. The methoxydiphenylphosphine ligands in [RhBr2(NO){P(OMe)Ph2}2] are cis-disposed whereas the larger cis-propoxydiphenylphosphine ligands in [RhBr2(NO){P(OPri)Ph2}2] are mutually trans. The nitrosyl group in trans-[RhBr2(NO){P(OPri)Ph2}2] eclipses an Rh-P axis but in cis-[RhBr2(NO){P(OMe)Ph2}2] it is staggered with respect to the P-Rh-P linkage. The isomeric behaviour of nitrosyl complexes of type [RhX2(NO)L2] (X = halogen, L = phosphorus donor ligand) is rationalized in terms of the size of the ligand L. 相似文献
19.
Conversion of Nitric Oxide into Nitrous Oxide as Triggered by the Polarization of Coordinated NO by Hydrogen Bonding
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Chuan‐Hung Chuang Prof. Wen‐Feng Liaw Prof. Chen‐Hsiung Hung 《Angewandte Chemie (International ed. in English)》2016,55(17):5190-5194
Reduction of the {Co(NO)}8 cobalt–nitrosyl N‐confused porphyrin (NCP) [Co(CTPPMe)(NO)] ( 1 ) produced electron‐rich {Co(NO)}9 [Co(CTPPMe)(NO)][Co(Cp*)2] ( 2 ), which was necessary for NO‐to‐N2O conversion. Complex 2 was NO‐reduction‐silent in neat THF, but was partially activated to a hydrogen‐bonded species 2 ??? MeOH in THF/MeOH (1:1, v/v). This species coupling with 2 transformed NO into N2O, which was fragmented from an [N2O2]‐bridging intermediate. An intense IR peak at 1622 cm?1 was ascribed to ν(NO) in an [N2O2]‐containing intermediate. Time–course ESI(?) mass spectra supported the presence of the dimeric [Co(NCP)]2(N2O2) intermediate. Five complete NO‐to‐N2O conversion cycles were possible without significant decay in the amount of N2O produced. 相似文献
20.
Susie Douglas Mary F. Mahon Michael K. Whittlesey 《Journal of organometallic chemistry》2005,690(23):5027-5035
Addition of excesses of N-heterocyclic carbenes (NHCs) IEt2Me2, IiPr2Me2 or ICy (IEt2Me2 = 1,3-diethyl-4,5-dimethylimidazol-2-ylidene; IiPr2Me2 = 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene; ICy = 1,3-dicyclohexylimidazol-2-ylidene) to [HRh(PPh3)4] (1) affords an isomeric mixture of [HRh(NHC)(PPh3)2] (NHC = IEt2Me2 (cis-/trans-2), IiPr2Me2 (cis-/trans-3), ICy (cis-/trans-4) and [HRh(NHC)2(PPh3)] (IEt2Me2(cis-/trans-5), IiPr2Me2 (cis-/trans-6), ICy (cis-/trans-7)). Thermolysis of 1 with the aryl substituted NHC, 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene (IMesH2), affords the bridging hydrido phosphido dimer, [{(PPh3)2Rh}2(μ-H)(μ-PPh2)] (8), which is also the reaction product formed in the absence of carbene. When the rhodium precursor was changed from 1 to [HRh(CO)(PPh3)3] (9) and treated with either IMes (=1,3-dimesitylimidazol-2-ylidene) or ICy, the bis-NHC complexes trans-[HRh(CO)(IMes)2] (10) and trans-[HRh(CO)(ICy)2] (11) were formed. In contrast, the reaction of 9 with IiPr2Me2 gave [HRh(CO)(IiPr2Me2)2] (cis-/trans-12) and the unusual unsymmetrical dimer, [(PPh3)2Rh(μ-CO)2Rh(IiPr2Me2)2] (13). The complexes trans-3, 8, 10 and 13 have been structurally characterised. 相似文献