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1.
The preparation and characterisation of the complexes [Co2(CO)4(PMe3)2][Co2(CO)6](Me3SiC2C2SiMe3) (4), [Co2(CO)4(dppm)][Co2(CO)6](Me3SiC2C2H) (5), [Co2(CO)4(dppa)][Co2(CO)6](Me3SiC2C2SiMe3) (6), [Co2(CO)4(dppm)]2[Co2(CO)6](Me3SiC2CCC2C2SiMe3) (7) and [{SiMe3(Co2(CO)4(dppm))C2}2(HCC)(1,3,5-C6H3)] (8) are described. An electrochemical study of the complexes 5-8 and of the related [Co2(CO)4(dppm)]2(Me3SiC2(CC)2C2SiMe3) (1), [Co2(CO)4(dppa)]2(Me3SiC2C2SiMe3) (2) and [{SiMe3(Co2(CO)4(dppm))C2}(HCC)2(1,3,5-C6H3)] (3) is presented by means of the cyclic and square-wave voltammetry techniques. Crystals of 8 suitable for single-crystal X-ray diffraction were grown and the molecular structure of this compound is discussed.  相似文献   

2.
The reactions of N,N-dimethylaminopropyl chalcogenolates with platinum(II) compounds have been carried out and complexes of the types [PtCl(ECH2CH2CH2NMe2)]2 (1) (E = S (1a) and Se (1b)), [Pt(ECH2CH2CH2NMe2)2]n (2) (E = S (2a) and Se (2b)), [(PtCl2)2{(Me2NCH2CH2CH2E)2}]n (3), [PtX(SeCH2CH2CH2NMe2)]2 (4) (X = SePh (4a) and OAc (4b)) and [PtCl(ECH2CH2CH2NMe2)(PR3)]n (5) (E = S, Se, Te) have been isolated. These complexes have been characterized by elemental analysis, IR, UV-Vis, NMR (1H, 13C, 31P, 77Se, 195Pt) spectroscopy and FAB mass spectral data. The structures of [PtCl(SeCH2CH2CH2NMe2)]2 (1b) and [PtCl(SCH2CH2CH2NMe2)(PPr3)]2 (5a) have been established by single crystal X-ray diffraction data. Both the molecules have dimeric structures. In 1b, two platinum atoms are held together by symmetrically bridging Se atoms of the chelating selenolate groups. In 5a, two thiolates form a four-membered Pt2S2 bridge with dangling NMe2 groups.  相似文献   

3.
The ansa-titanocene complexes, [Ti{Me2Si(η5-C5Me4)(η5-C5H3R)}Cl2] (R = Me (5), iPr (6), tBu (7), SiMe3 (8)), were obtained from the reaction of Li2{Me2Si(C5Me4)(C5H3R)} (R = Me (1), iPr (2), tBu (3), SiMe3 (4)) with [TiCl4(THF)2], respectively. Compounds 5-8 have been tested as catalysts in the polymerization of ethylene and compared with the ansa-titanocene complexes [Ti{Me2Si(η5-C5H4)2}Cl2] and [Ti{Me2Si(η5-C5Me4)(η5-C5H4)}Cl2]. The resulting polyethylene showed molecular weights of about 200 000 g mol−1 and polydispersity values of approximately 3. In addition, the molecular structure of 6 has been determined by single crystal X-ray diffraction studies.  相似文献   

4.
Dimethyl platinum(II) complexes [PtMe2(NN)] {NN = bu2bpy (4,4′-di-tert-butyl-2,2′-bipyridine) (1a), bpy (2,2′-bipyridine) (1b), phen (1,10-phenanthroline) (1c)} reacted with commercial 3-bromo-1-propanol in the presence of 1,3-propylene oxide to afford cis, trans- [PtBrMe2{(CH2)3OH}(NN)] (NN = bu2bpy (2a), bpy (2b), phen (2c)). On the other hand, [PtMe2(NN)] (1a)-(1b) reacted with the trace of HBr in commercial 3-bromo-1-propanol to give [PtBr2(NN)] (NN = bu2bpy (3a), bpy (3b)). The reaction pathways were monitored by 1H NMR at various temperatures. Treatment of 1a-1b with a large excess of 3-bromo-1-propanol at −80 °C gave the corresponding methyl(hydrido)platinum(IV) complexes [PtBr(H)Me2(NN)] (NN = bu2bpy (4a), bpy (4b)) via the oxidative addition of dimethyl platinum(II) complexes with HBr. The complexes [PtBr(H)Me2(NN)] decomposed by reductive elimination of methane above −20 °C for bu2bpy and from −20 to 0 °C for bpy analogue to give methane and platinum(II) complexes [PtBrMe(NN)] (5a)-(5b) and then decomposed at about 0 °C to yield [PtBr2(NN)] and methane. When the reactions were performed at a molar ratio of Pt:RX/1:10, the corresponding complexes [PtBrMe(NN)] (5a)-(5b) were also obtained. The crystal structure of the complex 3b shows that platinum adopts square planar geometry with a twofold axis through the platinum atom. The Pt…Pt distance (5.164 Å) is considerably larger than the interplanar spacing (3.400 Å) and there is no platinum-platinum interaction.  相似文献   

5.
The dicarbonyl and diphosphine complexes of the type (η5-C5H5)Fe(L)2ER3 (L2 = (CO)2 (a), (Ph2P)2CH2 (b); ER3 = CH3 (1a/b); SiMe3 (2a/b), GeMe3 (3a/b), SnMe3 (4a/b)) were synthesized and studied electrochemically. Cyclic voltammetric studies on the dicarbonyl complexes 1a-4a revealed one electron irreversible oxidation processes whereas the same processes for the chelating phosphine series 1b-4b were reversible. The Eox values found for the series 1a-4a were in the narrow range 1.3-1.5 V and in the order Si > Sn ≈ Ge > C; those for 1b-4b (involving replacement of the excellent retrodative π-accepting CO ligands by the superior σ-donor and poorer π-accepting phosphines) have much lower oxidation potentials in the sequence Sn > Si ≈ Ge > C. This latter oxidation potential pattern relates directly to the solution 31P NMR chemical shift data illustrating that stronger donation lowers the Eox for the complexes; however, simple understanding of the trend must await the results of a current DFT analysis of the systems.  相似文献   

6.
Reactions of [(p-cymene)RuCl2]2 (1a) with dpmp ((Ph2PCH2)2PPh) in the absence or presence of KPF6 afforded the ionic complexes [{(p-cymene)RuCl2}(dpmp-P1,P3;P2){RuCl(p-cymene)}](X) (2a1: X=Cl; 2a2: X=PF6). A (p-cymene)RuCl moiety constructs a 6-membered ring coordinated by two terminal P atoms of the dpmp ligand and another one binds to a central P atom of the ligand. Reactions of [(C6Me6)RuCl2]2 (1b) with an excess of dpmp in the presence of KPF6 gave a 4-membered complex [(C6Me6)RuCl(dpmp-P1,P2)](PF6) (3b), chelated by a terminal and a central P atom and another terminal atom is free. Use of Ag(OTf) instead of KPF6 gave [{(C6Me6)RuCl2(dpmp)Ag} 2](OTf)2 (5b) that the Ag atoms were coordinated by a terminal and a central P atom of each dpmp ligand. Reaction with an equivalent of dpmp in the presence of KPF6 gave [{(C6Me6)RuCl}(dpmp-P1,P2;P3){(C6Me6)RuCl2}](PF6) 4b. Complex has a structure that the (C6Me6)RuCl2 moiety coordinated to the free P atom of 3b. Complex 3b was treated with MCl2(cod) (M=Pd, Pt), [Pd(MesNC)4](PF6)2 (MesNC=2,4,6-Me3C6H2NC) or [Pt2(XylNC)6](PF6)2 (XylNC=2,6-Me2C6H3NC), generating [{(C6Me6)RuCl(dpmp)}2MCl2](PF6)2 (8b: M=Pd; 9b: M=Pt), [{(C6Me6)RuCl(dpmp)}2{Pt(MesNC)2}](PF6)4 (10b) and [{(C6Me6)RuCl(dpmp)}2{Pt2(XylNC)4}](PF6)4 (11b), respectively. Complex 3b reacted readily with [Cp*MCl2]2 (M=Rh, Ir) or AuCl(SC4H8), affording the corresponding hetero-binuclear complexes [{(C6Me6)RuCl}(dpmp-P1,P2;P3)(MCl2Cp*](PF6) (6b: M=Rh; 7b: M=Ir) and [{(C6Me6)RuCl}(dpmp-P1,P2;P3)(AuCl)](PF6) (12b). These complexes have two chiral centers. Some complexes were separated as two diastereomers by successive recrystallization. The structures of 3b, 5b, 6b, 8b and 12b were confirmed by X-ray analyses.  相似文献   

7.
Phosphorus-carbon bond is formed via: (i) the apparent HCCH insertion into Ir-P bond to produce Ir-CHCH-PPh3 group and (ii) the activation of the ring-methyl group of the coordinated Cp* (C5Me5 −) to produce Ir(η5-C5Me4CH2-PPh3) group from reactions of iridium(III)-Cp* complexes, [Cp*IrL3]n+ (n=1, 2); Cp*=C5Me5 −; L3=Cl(PPh3)2 (3), (CH3CN)3 (5). The following new P-C bond containing iridium(III) complexes have been prepared: [Cp*Ir(-CHCH-PPh3)Cl(PPh3)]+ (4) from 3 with HCCH; [Ir(η5-C5Me4CH2-PPh3)(H)(PPh3)2]2+ (6) from 5 with PPh3; [Cp*Ir(-CHCH-PPh3)2(PPh3)]2+ (7) from 5 with HCCH and PPh3; [Ir(η5-C5Me4CH2-PPh3)(-CHCH-PPh3)Cl(PPh3)]2+ (8) from [Ir(η5-C5Me4CH2-PPh3)(Cl)(PPh3)2]2+ (6-Cl) with HCCH; [Ir(η5-C5Me3(1,3-CH2-PPh3)2(H)(PPh3)2)]3+ (10) from [Ir(η5-C5Me4CH2-PPh3)(NCCH3)2(PPh3)]3+ (9) with PPh3; [Ir(η5-C5Me4CH2-PPh3)(-CHCH-PPh3)2(PPh3)]3+ (11) from 9 with HCCH and PPh3.  相似文献   

8.
Metal-sulfur complex fragments, to which small molecules like N2, N2H2, N2H4, NH3, or CO can bind, are desirable model compounds concerning enzymatic N2 fixation.This paper reports on the effects of the phosphane co-ligand on formation and reactivity of [Ru(L)(PR3)(`N2Me2S2')] [`N2Me2S2'2−=1,2-ethanediamine-N,N-dimethyl-N,N-bis(2-benzenethiolate)(2−)] complexes with nitrogenase relevant ligands, especially N2, N2H4, NH3, and CO.Treatment of [Ru(NCCH3)4Cl2] with Li2`N2Me2S2', excessive LiOMe, bulky PPh3 or PCy3, respectively, led to the formation of two series of [Ru(L)(PR3)(`N2Me2S2')] complexes [for R=Ph: 1b, 1c (L=NCCH3), 6b (L=N2H4), 7b (L=N2), 8b1-3 (L=CO), 9b (L=NH3); for R=Cy: 1a (L=NCCH3), 6a (L=N2H4), 7a (L=N2), 8a (L=CO), 9a (L=NH3)]. While the use of PPh3 (θ=145°) yielded cis,trans and cis,cis isomers of [Ru(NCCH3)(PPh3)(`N2Me2S2')] (1b, 1c), no isomer formation was observed with the bulkier phosphane PCy3 (θ=170°). Sterically less demanding phosphanes (θ=118-132°) afforded bisphosphane complexes [Ru(PR3)2(`N2Me2S2')] [2d (R=Me), 2e (R=Et), 2f (R=nPr), and 2g (R=nBu)], which were practically inert and could only be converted in two cases and under drastic reaction conditions into the CO complexes [Ru(CO)(PR3)(`N2Me2S2')] [4e (R=Et), 4f (R=nPr)]. The chelating bidentate phosphane dppe (bisdiphenylphosphanoethane) yielded exclusively the mononuclear complex [Ru(dppe)(`N2Me2S2')] (3).  相似文献   

9.
The reaction of alkyn-1-yl(vinyl)silanes R2Si(CCR1)CHCH2 [R = Me (1), Ph (2); R1 = tBu (a), Ph (b), SiMe3 (c)] with 9-borabicyclo[3.3.1]nonane in a 1:1 ratio affords the 1-silacyclopent-2-ene derivatives 4a-c (R = Me) and 5a-c (R = Ph) as a result of selective intermolecular 1,2-hydroboration of the vinyl group, followed by intramolecular 1,1-organoboration of the alkynyl substituent. The analogous reaction sequence converts the alkyn-1-yl(allyl)dimethylsilanes 3a,c into the 1-silacyclohex-2-ene derivatives 7a,c. All reactions were monitored by 29Si NMR spectroscopy and the structural assignment of the final products was based on multinuclear magnetic resonance data (1H, 11B, 13C and 29Si NMR). The molecular structure of 6a was determined by X-ray analysis.  相似文献   

10.
Single crystals of three derivatives of the structurally still incompletely characterized coordination polymer [(Me3Sn)4Ru(CN)6] 1b have been prepared and subjected to crystallographic studies: [1b · 4H2O]=2b forms stacks of puckered 2[Ru{μ-CNSn(Me3)NC}2] sheets interlinked by hydrogen bonds in making use of two additional CNSn(Me3)OH2 ligands and quasi-zeolitic water. Mild drying of 2b leads to the “missing link” between 1b and 2b, [1b · 2H2O], 3b. The structure of [1b · 2tp] (tp=4-thiopyridone) consists of a three-dimensional, negatively charged host framework comprising (via Sn-S bonds) one “aromatic” thione linkage and a [Me3Sn · tp]+guest ion involving a more zwitterionic form of tp. Slow uptake of Me3SnCl from the gas phase by an aqueous solution of K4[Ru(CN)6] and tp afforded the novel assembly [1b · 2H2O · 0.8pms · 0.2pds] (pms/pds=4,4-dipyridylmono-/disulfide), the supramolecular architecture of which resembles that of 2b. Bridging pms or pds molecules occupy equivalent interlayer sites, and the pms/pds ratio is likely to vary. At least three further assemblies containing again 1b and either tp or pds/pms have likewise been isolated, however, not as single crystals.  相似文献   

11.
Activation of the B-H σ-bond of amine-boranes on the chromium(0) center of arene chromium tricarbonyl complexes (η6-arene)Cr(CO)3 (arene = fluorobenzene, 1a; benzene, 1b and mesitylene, 1c) has been studied. Photolysis of 1b in presence of ammonia-borane (H3N·BH3, AB) and tert-butylamine-borane (tBuH2N·BH3, TBAB) resulted in H2 evolution and precipitation of a BNHx polymer. On the other hand, photolysis in the presence of trimethylamine-borane (Me3N·BH3, TMAB) resulted in the formation of a σ-borane complex (2) along with Cr(CO)5(η1-HBH2·NMe3) (3). The σ-borane complexes (η6-arene)Cr(CO)2(η1-HBH2·NMe3) (arene = fluorobenzene, 2a; benzene, 2b and mesitylene, 2c) were characterized in solution by 1H, 11B, and 13C NMR spectroscopy. Electron withdrawing substituents on the arene ring provide the more stable σ-borane moiety in this series of complexes.  相似文献   

12.
The synthesis and structural characterization of the two novel unsolvated heteroleptic ytterbium compounds DanipYb(TpMe,Me)Cl (1) and DanipYb(TpMe,Me)CH2SiMe3 (2) by simple salt metathesis reaction is reported [Danip = 2,6-di(o-anisol)phenyl); TpMe,Me = hydrotris(3,5-dimethyl-pyrazolyl)borate]. In the molecular structure of 2 a flexible bonding mode of the donor-functionalized terphenylic ligand is observed.  相似文献   

13.
The ligand hydrotris(1,4-dihydro-3-methyl-4-phenyl-5-thioxo-1,2,4-triazolyl)borato (TrPh,Me) was synthetized as natrium salt and the complexes [Zn(TrPh,Me)2] · 7.5H2O · 1.5CH3CN (2a), [Zn(TrPh,Me)2] · 8DMF (2b), [Co(TrPh,Me)2] · 8DMF (3a), [Ni(TrPh,Me)2] · H2O · 6DMSO (4a), [Bi(TrPh,Me)2]NO3 (5), have been isolated and structurally characterized by X-ray diffraction. In the zinc derivatives the ligand adopts different denticity and coordination modes, η2 and [S2] for 2a and η3 and [N3] for 2b, depending on the crystallization solvent, giving rise to tetrahedral and octahedral geometry, respectively. In the octahedral cobalt and nickel complexes the ligand is η3 and [N3] coordinated whereas in the bismuth complex the η3 and [S3] coordination is exhibited.  相似文献   

14.
The reactions of InCl3 with two and three equivalents of lithium (2-dimethylaminomethyl)pyrrolate (1) in diethyl ether solutions afford In[C4H3N(CH2NMe2)]2Cl (2) and In[C4H3N(CH2NMe2)]3 (3) in 92% and 50% yield, respectively. Subsequent reactions of 2 with MeLi and Li(CCPh) yield In[C4H3N(CH2NMe2)]2Me (4) and In[C4H3N(CH2NMe2)]2(CCPh) (5), respectively. All compounds were confirmed by 1H and 13C NMR spectroscopy and compounds 3, 4, and 5 were further characterized by single-crystal X-ray crystallography. Compounds 2, 3, and 4 showed moderate catalytic activity toward the ring-opening polymerization of ε-caprolactone.  相似文献   

15.
The β-diketiminato zinc halide [Me2NN]ZnCl2Li(THF)3 (1) is prepared in 51% isolated yield by addition of the lithium β-diketiminate Li[Me2NN] to ZnCl2 in THF. Reaction of 1 with 2 equiv. of the thallium thiolate TlSCy provides {[Me2NN]Zn(μ-SCy)2Tl}2 (2), a TlSCy adduct of [Me2NN]ZnSCy, as colorless crystals in 51% yield. Reaction of 1 with 1 equiv. TlSR provides the dinuclear {[Me2NN]Zn(μ-SR)}2 (R = Cy (3), tBu (4)) which possess unsymmetrically bridging thiolate ligands with pairs of dissimilar Zn-S distances in the solid state (2.350(3) and 2.417(3) Å for 3; 2.312(1) and 2.415(1) Å for 4). Reaction of 1 with LiSCPh3 results in the mononuclear zinc thiolates [Me2NN]ZnSCPh3(THF) (5) and [Me2NN]ZnSCPh3 (6) with shorter, but similar Zn-SR distances of 2.225(2) and 2.214(1) Å. Variable temperature 1H NMR studies of 3 and 4 in CDCl3 suggest that the aliphatic thiolates exist predominately as monomeric species in solution near room temperature, though at −50 °C two different β-diketiminato species are observed for 3. Thiolate exchange among 3, 4, and 6 also takes place on the NMR timescale near room temperature. Both 4 and 6 undergo transnitrosylation with CySNO in CDCl3 to give {[Me2NN]ZnSCy}2 (3) and the corresponding S-nitrosothiol tBuSNO or Ph3CSNO. Nitric oxide does not react with 4 or 6 under anaerobic conditions, but in the presence of O2, NO cleaves the zinc-thiolate bond of 4 to rapidly give tBuSNO. Similarly, anaerobic NO2 reacts with 4 to give tBuSNO providing insight into the active nitrogen oxide species capable of cleaving Zn-SR bonds.  相似文献   

16.
The synthesis and X-ray crystal structures of the following bis(amidinate)-substituted boron halides are reported: 1,3-C6H4[C{N(SiMe3)}2BCl2]2 (3), 1,4-C6H4[C{N(SiMe3)}2BCl2]2 (4), 1,4-C6H4[C{N(SiMe3)}2B(Ph)Cl]2 (5), 1,4-C6H4[C{NCy}2BCl2]2 (6), and 1,4-C6H4[C{NCy}2B(Ph)Cl]2 (7). Compounds 3-5 were prepared by trimethylsilyl chloride elimination, while 6 and 7 were prepared via salt metathesis reactions of the appropriate dilithium bis(amidinates) with BCl3 or PhBCl2. The molecular structures of complexes 3, 5, and 6 were determined by single-crystal X-ray diffraction, along with that of the free bis(amidine) 1a.  相似文献   

17.
Reactions of HfCl4 with 2 and 3 equiv. of Li[C4H3N(CH2NMe2)-2] in toluene afford HfCl2[C4H3N(CH2NMe2)-2]2 (1) and HfCl[C4H3N(CH2NMe2)-2]3 (2), respectively. Transmetallation reaction of 1 with 2 equiv. of MeLi results in a hafnium dimethyl compound HfMe2[C4H3N(CH2NMe2)-2]2 (3). A variable-temperature 1H NMR spectroscopic study shows that the activation energy for the dissociation/association of the NMe2 units of compound 2 in solution is ca. 13.6 kcal/mol. Compounds 1-3 are characterized by NMR spectroscopy and single crystal X-ray diffraction. A polymerization study shows that compounds 1 and 3 exhibit moderate activity toward ethylene in the presence of TIBA and MAO.  相似文献   

18.
The electrochemical behavior of the Pt(II)-based Baeyer-Villiger catalysts of the general formulae [Pt(μ-OH)(PP)]2(BF4)2 (PP = dppe (1a), 2Fdppe (1 b), 4Fdppe (1c), dfppe (1d), dmpe (1e), depe (1f), dippe (1g), dtbpe (1h)) and [Pt(OH2)2(PP)](OTf)2 (PP = dppe (2a), 2Fdppe (2b), 4Fdppe (2c), dfppe (2d)) is reported. They exhibit irreversible reduction processes whose potentials reflect the Lewis acidity of the metal centres, showing (for the aromatic diphosphine complexes) overall relations with the number of fluorine atoms, with JPt-P, with the ν(CN) coordination shift of a ligand isocyanide probe and with the catalytic activity. Single-crystal X-ray diffraction analyses were carried out for [Pt(μ-OH)(4Fdppe)]2(BF4)2 (1c) and [Pt(μ-OH) (dippe)]2(BF4)2 (1g).  相似文献   

19.
《Inorganica chimica acta》2004,357(10):3119-3123
Fused double-cluster [(η5-C5Me5)IrB18H18(PH2Ph)] (8), from syn-[(η5-C5Me5)IrB18H20] (1) and PH2Ph, retains the three-atoms-in-common cluster fusion intimacy of 1, in contrast to [(η5-C5Me5)HIrB18H19(PHPh2)] (6), from PHPh2 with 1, which exhibits an opening to a two atoms-in-common cluster fusion intimacy. Compound 8 forms via spontaneous dihydrogen loss from its precursor [(η5-C5Me5)HIrB18H19(PH2Ph)] (7), which has two-atoms-in-common cluster-fusion intimacy and is structurally analogous to 6.  相似文献   

20.
The reaction of OCO chelated organolithium compound LLi (1) (L = 2,6-(t-BuOCH2)2C6H3) with SbCl3 in 2:1 molar ratio gave diorganoantimony compound L2SbCl (2). The reactions of the compound 2 with selected lithium acetylides resulted to the Sb←O coordinated antimony acetylides L2Sb(CCR) (R = Ph, (3), t-Bu (4), Me3Si (5)). All studied compounds were characterized by the help of elemental analysis, 1H and 13C NMR spectroscopy and IR spectroscopy. Molecular structures of the compounds 2-4 were determined using the X-ray diffraction technique in the solid state.  相似文献   

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