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1.
The bidentate phosphine 2,11-bis(diphenylphosphinomethyl)benzo [c]phenanthrene ( 1 ) has been used to prepare the mononuclear, square planar complexes trans-[MX(CO)( 1 )] and trans-[M(CO)(CH3CN)( 1 )][BF4] (M = Rh, Ir; X = Cl, Br, I, NCS). It is found that the tendency of these complexes to form adducts with CO, O2 and SO2 is significantly lower than that of the corresponding Ph3P complexes. The oxidative-addition reactions of complexes trans-[IrX (CO) ( 1 )] with hydrogen halides give the six-coordinate species [IrHX2(CO) ( 1 )]. The complexes [IrH2I (CO) ( 1 )] and [IrH2L (CO) ( 1 )] [BF4] (L = CO and CH3CN) have been obtained from hydrogen and the corresponding substrates. The model compounds trans-[MCl (CO) (Ph2PCH2Ph)2] (M = Rh, Ir), trans-[Ir (CO) (CH3CN) (Ph2PCH2Ph)2] [BF4], [IrHCl2(CO)(Ph2PCH2Ph)2] and [IrH2(CO)2(Ph2PCH2Ph)2] [BF4] have been prepared and their special parameters are compared with those of the corresponding complexes of ligand 1 . The influence of the static requirements of this ligand on the chemistry of its rhodium and iridium complexes is discussed. 相似文献
2.
John R. Briggs Christopher Crocker Walter S. McDonald Bernard L. Shaw 《Journal of organometallic chemistry》1979,181(1):213-221
Five complexes of type cis-[PtCl2(PR3)Q] (PR3 =PMe3, PMe2Ph, PEt3; Q = CH2 CHOCOCH3 or CH2=CHCH2OCOCH3) have been prepared. The crystal structure of cis-[PtCl2[PME2Ph)(CH2=CHOCOCH3)] is described. Crystals of cis-[PtCl2(PME2Ph)(CH2-CHOCOCH3)] are triclinic, with a 8.441(4), b 13.660(5), c 7.697(3) Å, a 101.61(3)°, β 111.85(3)° γ 95.22(3)°, pP1, Z = 2. The structure was determined from 2011 reflections I σ 3σ (I) and refined to R = 0.037. The CH3COO grouping is syn to the cis-PMe2Ph ligand, with bond lengths of PtCl (trans to P) 2.367(3), PtCl (trans to olefin) 2.314(3), PtP 2.264(2), and PtC of 2.147(12) and 2.168(11) Å. The complexes cis-[PtCl2- (PR3)Q] were studied by variable temperature 1H and 31P NMR spectroscopy. Spectra of the vinyl acetate complexes were temperature dependent as a result of rotation about the platinum—olefin bond. The rotation was “frozen out” at ca. 240 K; for cis-[PtCl2(PME2Ph)(CH2=CHOCOCH3] ΔG≠ (rotation) 15.0 ± 0.2 kcal mol-1. NMR parameters for the rotamers are reported. NMR studies of the interaction between chloro-bridged complexes of type [Pt2Cl2(PR3)2] (PR3 = P-N-Pr3 or PMe2Ph) and vinyl acetate shows that even at low temperatures (213 K) equilibrium favours the bridged complex and the proportion of trans-[PtCl2(PR3)CH2=CHOCOCH3)] is very small e.g. 2%. The allyl acetate complexes cis-[PtCl2(PR3)(CH2=CHCH2OCOCH3)] showed only one rotamer over the range 333–213 K. Reversible dissociation of cis-[PtCl2(PMe2Ph)- (CH2=CHCH2OCOCH3)] to [Pt2Cl4(PMe2Ph)2] + allyl acetate was studied at ambient temperature. At low temperatures e.g. 213–190 K addition of allyl acetate to a CDCl3 solution of [Pt2Cl2(P-n-Pr3)2] reversibly gave some olefin complex trans-[PtCl2(P-n-Pr3)(CH2=CHCH2OCOCH3)] and some O-bonded complex trans-[PtCl2(P-n-Pr3)(CH2=CHCH2OCOCH3)]. 相似文献
3.
Reaction of Pentelidene Complexes with Diazoalkanes: Stabilization of Parent 2,3‐Dipnictabutadienes
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Dr. Michael Seidl Dr. Markus Stubenhofer Prof. Dr. Alexey Y. Timoshkin Prof. Dr. Manfred Scheer 《Angewandte Chemie (International ed. in English)》2016,55(45):14037-14040
The reaction of the phosphinidene complex [Cp*P{W(CO)5}2] ( 1 a ) with diphenyldiazomethane leads to [{W(CO)5}Cp*P=NN{W(CO)5}=CPh2] ( 2 ). Compound 2 is a rare example of a phosphadiazadiene ligand (R‐P=N?N=CR′R′′) complex. At temperatures above 0 °C, 2 decomposes into the complex [{W(CO)5}PCp*{N(H)N=CPh2)2] ( 3 ), among other species. The reaction of the pentelidene complexes [Cp*E{W(CO)5}2] (E=P, As) with diazomethane (CH2NN) proceeds differently. For the arsinidene complex ( 1 b ), only the arsaalkene complex 4 b [{W(CO)5}2{η1:2‐(Cp*)As=CH2}] is formed. The reaction with the phosphinidene complex ( 1 a ) results in three products, the two phosphaalkene complexes [{W(CO)5}2{η1:2‐(R)P=CH2}] ( 4 a : R=Cp*, 5 : R=H) and the triazaphosphole derivative [{W(CO)5}P(Cp*)‐CH2‐N{W(CO)5}=N‐N(N=CH2)] ( 6 a ). The phosphaalkene complex ( 4 a ) and the arsaalkene complex ( 4 b ) are not stable at room temperature and decompose to the complexes [{W(CO)5}4(CH2=E?E=CH2)] ( 7 a : E=P, 7 b : E=As), which are the first examples of complexes with parent 2,3‐diphospha‐1,3‐butadiene and 2,3‐diarsa‐1,3‐butadiene ligands. 相似文献
4.
《Polyhedron》1999,18(5):729-733
Equimolar quantities of [Mo (CO) (η2-RC2R′)2Cp] [BF4] (R=R′=Me Ph R=Me R′=Ph) and L L′ or L″ {L L′ or L″= [WI2 (CO){PhP(CH2CH2PPh2)2-PP′} (η2-RC2R′)]} (L R=R′=Me L′ R=R′=Ph L″ R=Me R′=Ph) react in CH2Cl2 at room temperature to give the new bimetallic complexes[Mo (CO) (L L′ or L″–P) (η2-RC2R′)Cp] [BF4] (1–9) via displacement of the alkyne ligand on the molybdenum centre The complexes have been characterised by elemental analysis IR and 1 H NMR spectroscopy and in selected cases by 31 P NMR spectroscopy. 相似文献
5.
Density functional theory calculations have been performed for understanding factors responsible for the different stabilities of particular isomers of [ReOX(N–O)2], where N–O represents carboxylate ligand chelating to the oxorhenium core through N and O atoms. DFT/B3LYP calculations have been carried out for all possible potential isomers of [ReO(OMe)(2-qc)2] (1), [ReOCl(2-qc)2] (2), [ReO(OMe)(1-iqc)2] (3), and [ReOCl(1-iqc)2] (4). Interestingly, complex 1 shows a very rare example of trans [O=Re–OMe] conformation with two chelating N,O-donor ligands in the equatorial plane, whereas the others were found to be the most common structure of [ReOX(N–O)2] with cis-N,N arrangement and chloride or methoxy ligand cis to the Re=O moiety. A thorough study of the calculated structures clearly shows that molecular structure of complexes [ReOX(N–O)2] is predominantly governed by multiply bonded oxo ligand, but the isomeric preferences may be tuned by careful selection of N–O ligands. 相似文献
6.
Two stereoisomers of cis-[Ru(bpy)(pynp)(CO)Cl]PF6 (bpy = 2,2′-bipyridine, pynp = 2-(2-pyridyl)-1,8-naphthyridine) were selectively prepared. The pyridyl rings of the pynp ligand in [Ru(bpy)(pynp)(CO)Cl]+ are situated trans and cis, respectively, to the CO ligand. The corresponding CH3CN complex ([Ru(bpy)(pynp)(CO)(CH3CN)]2+) was also prepared by replacement reactions of the chlorido ligand in CH3CN. Using these complexes, ligand-centered redox behavior was studied by electrochemical and spectroelectrochemical techniques. The molecular structures of pynp-containing complexes (two stereoisomers of [Ru(bpy)(pynp)(CO)Cl]PF6 and [Ru(pynp)2(CO)Cl]PF6) were determined by X-ray structure analyses. 相似文献
7.
Helmut Fischer Normen Szesni Gerhard Roth Nicolai Burzlaff Bernhard Weibert 《Journal of organometallic chemistry》2003,683(2):301-312
Displacement of tetrahydrofuran in [(CO)5M(THF)] (M=Cr, W) by the anion [CCC(X)Y]− (X=O; NR; Y=NR′2, Ph) followed by alkylation of the resulting metalate with [R″3O]BF4 (R″=Me, Et) offers a convenient and versatile route to π-donor-substituted allenylidene complexes, [(CO)5MCCC(XR″)Y]. Allenylidene complexes in which the terminal carbon atom of the allenylidene ligand constitutes part of a heterocycle are likewise accessible by this reaction sequence. Reaction of [(CO)5M(THF)] with Li[CCC(NMe)Ph]− and subsequent protonation of the metalate afford [(CO)5MCCC(NMeH)Ph] in high yield. As indicated by the spectroscopic data of the compounds and the X-ray analyses of three representative examples, these allenylidene complexes are best described as hybrids of allenylidene and zwitterionic alkynyl complexes with delocalisation of the electron pair at nitrogen towards the metal center. Dimethylamine reacts with the amino(phenyl)allenylidene complex [(CO)5CrCCC(NMe2)Ph] (7a) by addition of the amine across the CαCβ bond to give selectively the E-alkenyl(amino)carbene complex [(CO)5CrC(NMe2)CHC(NMe2)Ph] (12). In contrast, the reaction of dimethylamine with the amino(methoxy)allenylidene complex [(CO)5CrCCC(NMe2)OMe] (1a) proceeds by addition of the amine to the Cγ atom and subsequent elimination of methanol to give the substitution product [(CO)5CrCCC(NMe2)2] (13). Triphenylphosphane neither adds to the Cα nor the Cγ atom of 7a but upon irradiation displaces a CO ligand to form a cis-allenylidene(tetracarbonyl)phosphane complex 15. 相似文献
8.
《Journal of organometallic chemistry》1987,331(2):207-219
The hydrido complexes cis-[HTa(CO)4P2] (P2 Ph2PCH2CH2PPh2), HTa-(CO)3Pm (Pm P3: PhP(CH2CH2PPh2)2, P4: [Ph2PCH2CH2PPhCH2]2, PP3: P(CH2CH2PPh2)3) have been obtained from the photo-chemically produced complexes [Et4N][Ta(CO)4Pm] by ion-exchange chromatography on silica gel. The anionic and neutral complexes have been characterized by IR and 31P and 1H NMR spectroscopy. The temperature-dependent 1H(hydride)-31P NMR coupling patterns are interpreted in terms of a hydride-capped octahedral structure with restricted migration of the H− ligand between the octahedral faces. 相似文献
9.
Piotr Jaunky 《Journal of organometallic chemistry》2004,689(4):801-810
The ruthenium and iron dicarbonyl complexes Ru(MeP(CH2CH2PMe2)2)(CO)2 (1), Ru(MeP(CH2CH2CH2PMe2)2)(CO)2 (2) and Fe(MeP(CH2CH2CH2PMe2)2)(CO)2 (3) bearing strong donor tridentate phosphine ligands were prepared and fully characterised. The structures of the complexes have been established by X-ray diffraction studies. Oxidative addition of MeI to 1-3 proceeds instantaneously at room temperature and affords the corresponding octahedral cationic complexes fac,cis-[RuMe(MeP(CH2CH2PMe2)2)(CO)2]I (5a) and mer,cis-[RuMe(MeP(CH2CH2PMe2)2)(CO)2]I (5b), mer,trans-[MMe(MeP(CH2CH2CH2PMe2)2)(CO)2]I (6a (M=Ru); 7a (M=Fe)) and mer,cis-[MMe(MeP(CH2CH2CH2PMe2)2)(CO)2]I (6b (M=Ru); 7b (M=Fe)), respectively. The triphosphine preferentially adopts a facial arrangement in the case of the ethylene bridged tridentate ligand (5a) and a meridional arrangement in the case of the trimethylene bridged ligand (6a-7b). mer,cis-[RuMe(MeP(CH2CH2CH2PMe2)2)(CO)2]I (6a) undergoes CO insertion to the acetyl complex mer, trans-[Ru(COMe)(MeP(CH2CH2CH2PMe2)2)(CO)2]I (8). Attempts to produce a ketene complex from the deprotonation of 8 were not successful. The acetyl protons in 8 show very low acidity and no reaction occurred when the complex was reacted with bases such as DBU, BEMP (2-tert-Butylimino-2-diethylamino-1,3-dimethyl-perhydro-1,3,2-diazaphosphorine) or LDA. 相似文献
10.
N.E. Kolobova A.B. Antonova O.M. Khitrova M.Yu. Antipin Yu.T. Struchkov 《Journal of organometallic chemistry》1977,137(1):69-78
The novel complexes CpRe(CCHPh)(CO)2 and Cp2Re2(μ-CCHPh)(CO)4 containing a terminal and a bridging phenylvinylidene ligand respectively and the binuclear complex Cp(CO)2Re[CC(Ph)C(Ph)CH2]Re(CO)2Cp were obtained in the reaction of CpRe(CO)3 with PhCCH.According to an X-ray study of the latter complex the unusual bridging ligand is η1-bonded to one Re atom and η2-bonded to the other. 相似文献
11.
UV irradiation of [Et4N] [V(CO)6] in the presence of the tripod ligands (L) MeC(CH2PPh2)3 (cp3) and P(CH2CH2PPh2)3 (pp3) yields [Et4N] [V(CO)5L], cis-[Et4N] [V(CO)4L] and mer-[Et4N] [V(CO)3L] (where the meridional configuration for L = cp3 is uncertain). Except for [Et4N] [V(CO)5cp3], all these species were isolated. The complexes are characterized by their IR, 31P and 51V NMR spectra. 相似文献
12.
《Journal of organometallic chemistry》1991,410(1):C9-C12
The triisocyanide ligand CH3C(CH2NC)3, time, reacts with metal carbonyls M(CO)x (M = Cr, W, χ = 6; M = Fe, χ = 5) to give the triply metal carbonyl substituted complexes CH3C[CH2NCM(CO)x]3 (M = Cr, W, χ = 5; M = Fe, χ = 4). CH3C[CH2NCW(CO)5]3 was characterized by an X-ray structure determination. 相似文献
13.
Sofia I. Pascu Karl S. Coleman Nicholas H. Rees 《Journal of organometallic chemistry》2005,690(6):1645-1658
Treatment of the bulky iminophosphine ligand [Ph2PCH2C(Ph)N(2,6-Me2C6H3)] (L) with [M(CH3CN)2(ligand)]+n, where for M = Pd(II): ligand = η3-allyl, n = 1, and for M = Rh(I), ligand: 2(C2H4), 2(CO) or cod, n = 0, yields the mono-cationic iminophosphine complexes [Pd(η3-C3H5)(L)][BF4] (1), [Rh(cod)(L)][BF4] (2), [Rh(CO)(CH3CN)(L)][BF4] (3), and cis-[Rh(L)2][BF4] (4). All the new complexes have been characterised by NMR spectroscopy and X-ray diffraction. Complex 1 shows moderate activity in the copolymerisation of CO and ethene but is inactive towards Heck coupling of 4-bromoacetophenone and n-butyl acrylate. 相似文献
14.
Verena Blase 《Journal of organometallic chemistry》2011,696(21):3337-3342
Reaction of cis-[ReCl(NHC)(CO)4] cis-[1] (NHC = NH,NH-substituted saturated cyclic diaminocarbene) with diphosphine (2-F-C6H4)2P-CH2CH2-P(C6H4-2-F)22 yields complex fac-[Re(NHC)(2)(CO)3]Cl fac-[3]Cl. Deprotonation of the NH,NH-NHC ligand in fac-[3]Cl with KOtBu leads to an intramolecular nucleophilic aromatic substitution of one fluorine atom from each -P(C6H4-2-F) group by the NHC ring nitrogen atoms with formation of complex fac-[4]Cl bearing a facially coordinated [11]ane-P2CNHC ligand. Reaction of cis-[MnBr(NHC)(CO)4] cis-[5] (NHC = NH,NH-substituted saturated cyclic diaminocarbene) with diphosphine 2 yields complex [MnBr(NHC)(2)(CO)2] [6] without substitution of the bromo ligand and with the phosphine donors from the bidentate diphosphine occupying one cis and one trans position to the NHC donor. 相似文献
15.
The complex mer-trans-[Mn(CO)3{P(OMe)2Ph}2X] (X = Cl, Br) is an intermediate in the conversion of fac-[Mn(CO)3{P(OMe)2,Ph}2,X] into mer- cis-[Mn(CO)2{P(OMe)2Ph}3X] in the presence of P(OMe)2Ph in benzene. No direct route between the latter two complexes could be detected kinetically. The results imply a trans carbonyl disposition as a prerequisite for higher carbonyl substitution in octahedral Mn1 carbonyl complexes. 相似文献
16.
Functionalization of the inert C? H bonds of unsaturated molecules by transition metal complex is an important means to form new C? C bonds. The functionalization is usually initiated by the ligand dissociation of a complex. In this paper we employ both ab initio and density functional methods to explore the influence of central metals, conformation, solvent and protonation on the ligand dissociation of the (hfac‐O,O)2M(L)(py) complexes [M=Rh(III) or Ir(III), hfac‐O,O=k2‐O,O‐1,1,1,5,5,5‐hexafluoroacetylacetonato, L=CH3, CH3CO2, (CH3CO)2CH, CH3O or OH, py=pyridine]. We demonstrate that ligand pyridine dissociates more easily than the "L" ligands under study in aprotic solvent and gas phase and the dissociation of pyridine is more facile in the trans‐conformation than in the cis‐isomer. These phenomena are rationalized based on electronic structure and molecular orbital interactions. We show that solvation only slightly stabilizes the complexes and does not change the ligand dissociation ordering. In particular, we show that pyridine is no longer the labile ligand in protic media. Instead, the oxygen‐containing ligands (apart from those like hfac that form a cyclic structure with the central metal) that coordinate to the central metal via oxygen atom become the labile ones. Finally our calculations indicate that hfac is a stable ligand, even in protic media. 相似文献
17.
Laurence D. Rosenhein William E. Newton John W. McDonald 《Journal of organometallic chemistry》1985,288(1):C17-C21
The new complexes [Et4N]2 [Mo(CO)4(SR)2] (R = Ph, Bz) have been prepared by reaction of [Et4N] [SR] with (norbornadiene)Mo(CO)4 at low temperature. The IR spectra and electrochemical behavior of these two species are different, perhaps implicating different conformational isomers with respect to the thiolate ligands. These complexes may prove to be valuable reagents for the synthesis of new heterometallic compounds, by virtue of their cis-monodentate thiolate ligands. 相似文献
18.
Alan Dobson David S. Moore Stephen D. Robinson Michael B. Hursthouse Lucy New 《Polyhedron》1985,4(6):1119-1130
The hydrides [MH(O2CCF3)(CO)(PPh3)2] (M = Ru or Os) react with disubstituted acetylenes PhCCPh and PhCCMe to afford vinylic products [M{C(Ph)CHPh}(O2CCF3)(CO)(PPh3)2] and [M{C(Ph)CHMe}(O2CCF3)(CO) (PPh3)2]/[M{C(Me)CHPh}(O2CCF3)(CO)(PPh3)2] respectively. Acidolysis of these products with trifluoroacetic acid in cold ethanol liberates cis-stilbene and cis-PhHCCHMe respectively thus establishing the cis-stereochemistry of the vinylic ligands. The complexes [M(O2CCF3)2(CO)(PPh3)2] formed during the acidolysis step undergo facile alcoholysis followed by β-elimination of aldehyde to regenerate the parent hydrides [MH(O2CCF3)(CO)(PPh3)2] and thereby complete a catalytic cycle for the transfer hydrogenation of acetylenes. The molecular structure of the methanol-adduct intermediate, [Ru(O2CCF3)2(MeOH)(CO)(PPh3)2] has been determined by X-ray methods and shows that the coordinated methanol is involved in H-bonding with the monodentate trifluoroacetate ligand [MEO-H---OC(O)CF3; O...O = 2.54 Å]. The hydrides [MH(O2CCF3)(CO) (PPh3)2]react with 1,4-diphenylbutadiyne to afford the complexes [M{C(CCPh)CHPh} (O2CCF3)(CO)(PPh3)2]. The ruthenium product, which has also been obtained by treatment of [RuH(O2CCF3)(CO)(PPh3)2] with phenylacetylene, has been shown by X-ray diffraction methods to contain a 1,4-diphenylbut-1-en-3-yn-2-yl ligand. The osmium complexes [Os(O2CCF3)2(CO)(PPh3)2], [OsH(O2CCF3)(CO)(PPh3)2] and [Os{C(CCPh)CHPh}(O2CCF3)(CO)(PPh3)2] all serve as catalysts for the oligomerisation of phenylacetylene. Acetylene reacts with [Ru(O2CCF3)2(CO)(PPh3)2] in ethanol to afford the vinyl complex [Ru(CHCH2)(O2CCF3)(CO)(PPh3)2]. 相似文献
19.
The complexes [MHCl(CO)(PPh3)3] (M = Ru or Os) readily undergo substitution at the site trans to the hydride ligand to afford phosphinite-, phosphonite-, or phosphite-containing products [MHCI(CO)(PPh3)2L] [L = P(OR)Ph2, P(OR)2Ph or P(OR)3 respectively; R = Me or Et]. The ruthenium complexes alone undergo further substitution to afford complex cations [RuH(CO)(PPh3)nL4?n]+ [n = 2, L = P(OMe)3; n = 1, L = P(OR)3; n = 0, L = P(OR)2Ph or P(OR)Ph2] which were isolated and characterised as their tetraphenylborate salts. Synthesis of the cationic complexes [IrHL5][BPh4]2 [L = P(OR)3, R = Me or Et] is also reported. Stereochemical assignments based on NMR data are given, and second order 31P and high field 1H NMR patterns are analysed. 相似文献
20.
Walter K. Dean Gary L. Simon Paul M. Treichel Lawrence F. Dahl 《Journal of organometallic chemistry》1973,50(1):193-207
The accidental but intriguing synthesis of acetatobis(triphenylphosphine)dicarbonylmanganese(I), (CH3CO2)Mn(CO)2[P(C6H5)3]2, has been accomplished by the reaction of NaMn(CO)5 with (CH3)3SiCl followed by the addition of triphenylphosphine and acetic acid. A three-dimensional single-crystal X-ray diffraction analysis has shown an octahedral-like molecule containing a symmetrically oxygen-chelating acetate group, the first such group to be reported in a metal carbonyl complex. The two triphenylphosphine ligands occupy mutually trans positions with the two carbonyl ligands possessing the remaining cis sites in the octahedral complex. The compound crystallizes with four molecules in a monoclinic unit cell of space group symmetry and of dimensions a = 17.744(2) Å, b = 9.692(1) Å, c = 20.004(2) Å, and β = 106.195(4)°. The relatively long MnO(acetate) bond lengths [2.066(6) and 2.069(7) Å] and the relatively short MnCO bond lengths [1.701(12) and 1.760(13) Å] and the relatively short MnP(C6H5)3 bond lengths [2.260(3) and 2.275(3) Å], compared to the corresponding MnCO and MnP(C6H5)3 bond lengths in other manganese carbonyl triphenylphosphine complexes, are rationalized on the basis that the acetate ligand in this molecule functions primarily as a σ-donor. 相似文献