Metal Complexes with Anionic Ligands of Elements of the Main Group IV. VII(1) Substitution Reactions of Carbonylnitrosyl and Nitrosyltrifluorophosphine Transition Metal Complexes with Trichlorostannid L-substitution by [SnCl3]? occurs if the nitrosyl complexes Co(NO)L3 and Fe(NO)2L2 (L = CO or PF3) are reacted with [N(C2H5)4][SnCl3] thermically in tetrahydrofuran as well as photochemically induced in methylenechloride. The complexes Co(NO)L3 yield the mono-substitution products [N(C2H5)4][Co(NO)L2SnCl3], with the iron compounds Fe(NO)2L2 only the disubstituted derivative [N(C2H5)4]2[Fe(NO)2(SnCl3)2] can be isolated. On the other hand CO substitution at (π-C5H5)Mo(NO)(CO)2 by UV irradiation did not suceed both with [SnCl3]? and with PF3. From the IR-spectroscopic data a leastly with PCl3 comparable π-acceptor ability is derived for the trichlorostannido ligand. 相似文献
Metal Complexes with Anionic Ligands of the Main Group IV Elements. IX. Reactions of Trichlorostannide and Trichlorogermide Ions with Complexes of Transition Metals in Low Oxidation States Carhonyl trichlorostannido- and carbonyl trichlorogermido-metalate complexes have been synthesized both by photochemical and thermical substitution reactions of [ECl3]? ions (E = Sn, Ge) with M(CO)6, (M = Cr, Mo, W), Fe(CO)5 Fe3(CO)12, Co2(CO)8, as well as with the metalcarbonyl derivatives (π-arene)M(CO)3, (M = Cr, Mo), (h5-C5,H5,)V(CO)4, Mn(CO)5,Cl, Co(NO)(CO)3, and Fe(NO)2,(CO)2. Mainly the bonding properties of the [ECl3]? ligands are discussed by means of i.r. spectroscopic investigations. The progress of the reactions and the necessary reaction conditions show that the nucleophilic properties oft both anions [ECl3]? are unexpectedly small. The slightly weaker hasicity of [SnCl3]? compared with [GeC13]? arreared, when both anions were reacted with Co2,(CO)8, forming the substitution product. [Co2,(CO)7,SnCl3]? and the products of a “base reaction” Cl3GcCo(CO)4, and [Co(CO)4]?. 相似文献
On Reactions of Subgroup. VI. Hexacarbonyls with Tin(II) and Germanium (II) Halides The neutral complexes M(CO)5SnX2 and M(CO)5GeCl2 (M = Cr, Mo, W; X = Cl, Br, J) have been prepared by a photochemical reaction between M(CO)6 and SnX2, or CsGeCl3 in THF. The reaction of these compounds with [N(CH3)4]X (X = Cl, Br, J) in THF was found to lead to a series of anions [M(CO)5SnX3]? or [M(CO)5GeCl3]? (M = Cr, Mo, W; X = Cl, Br, J), some of which have previously been prepared. The physical properties and IR-spectra of the above compounds are discussed. 相似文献
Metal Trifluorophosphine Complexes. XXXV. Alkyl-tetrakis(trifluorophosphine)cobalt Complexes. The preparation of the alkyl-tetrakis(trifluorophosphine)cobalt complexes RCo(PF3)4 (R = CH3 C2H5, C7H7) starting from [Co(PF3)4]? is only possible with very strong alkylating agents like oxonium salts, due to the low nucleophilicity of [Co(PF3)4]? anion. The complexes with R = CH3 and C2H5 are unpolar, very volatile, and thermally much more stable than the corresponding carbonyl complexes RCo(CO4). From spectroscopic studies a trigonal-bipyramidal structure is deduced. The electronegativity of the Co(PF3)4 part has been determined by NMR-measurements, which stress the unpolar nature of the carbon-cobalt bond. 相似文献
Metal Complexes with Anionic Ligands of Elements of the Main Group IV. VIII Pentacarbonyltrihalogenostannidometalate(O) Complexes of Chromium, Molybdenum, and Tungsten with Fluorine and Iodine Containing Trihalogenostannido Ligands In methylenechloride [As(C6H5)4][SnF3] readily reacts with the metalhexacarbonyls forming the arsoniumsalts of the pentacarbonyltrifluorostannidometalate(O) complexes, [M(CO)5SnF3]? (M ? Cr, Mo, W). Exclusively by the reaction of the intermediately formed complex Cr(CO)5THF only one pure triiodostannidometalate(O) Complex, [N(C2H5)4][Cr(CO)5SnJ3], could be isolated. The trihalogenostannidometalate(O) complexes [M(CO)5SnClX2]? (X ? F: M ? Cr, Mo, W; X ? J: M ? Cr) could be prepared by SnX2-insertion reactions of the [M(CO)5Cl]? complexes. The bonding properties of the halogenostannide ions are discussed on the bases of the IR spectra of their metalate(O) complexes. 相似文献
A number of stannylene complexes with different M: Sn ratios were obtained using various metals and substituents at the tin atom. The structures of the complexes were examined. A reaction of CpMn(CO)2THF with (Ph4As)+(SnCl3)? gave the ionic complex [Ph4As]+[CpMn(CO)2SnCl3]? (I). The action of C6F5MgBr on the complex C5H5Mn(CO)(NO)SnCl3 produced C5H5Mn(CO)(NO)Sn(C6F5)3 (II). Replacement of the Cl ions in the complex [CpFe(CO)2]2SnCl2 by phenylacetylenide groups gave rise to the neutral complex [CpFe(CO)2]2Sn(C≡CPh)2 (III). A reaction of (Dppm)PtCl2 (Dppm is 1,1-bis(diphenylphosphino)methane) with SnCl2 · 2H2O in the presence of diglyme yielded the ionic complex [η3-CH3O(CH2)2O(CH2)2OCH3)SnCl]+[(η 2-Dppm)Pt(SnCl3)3]? (IV). Transmetalation in a reaction of [(Dppe)2CoCl][SnCl3] · PhBr (Dppe is 1,2-bis(diphenylphosphino)ethane) with (Dcpd)PtCl2 (Dcpd is dicyclopentadiene) in the presence of SnCl2 afforded the ionic complex [Pt(Dppe)2]3[Pt(SnCl3)5]2 (V). Structures I–V were identified by X-ray diffraction. In these structures, the formally single bonds between the atoms of transition metals M (Mn, Fe, and Pt) and Main Group heavy elements (Sn and P) having vacant d orbitals are appreciably shortened. The M-Sn bond length in complexes II and III are virtually independent of the substituents at the tin atom and the Pt-Sn bond length in complexes IV and V is virtually independent of the Pt: Sn ratio. 相似文献
The binuclear nitrosylhalides of iron and cobalt react with cyanide to anionic complexes [M(NO)2(CN)2]? (M = Fe, Co). Substituted monomeric compounds M(NO)2LBr and Ni(NO)L2Br lead primarily under replacement of bromide to nonionic complexes M(NO)2LCN and Ni(NO)L2CN. In general these complexes react with more cyanide yielding anions [M(NO)2(CN)2]?, [Ni(NO)L(CN)2]? and [Ni(NO)(CN)3]2?. The paramagnetic dinitrosyliron compounds can be reduced to diamagnetic complexes by Na/Hg. A disproportion reaction of Co(NO)2P(C6H5)3CN forms a salt [Co(NO)2 · (P(C6H5)3)2][Co(NO)2(CN)2], a similar salt can be made by the reaction of Na[Co(NO)2(CN)2] with [Co(NO)2(NHP(C6H5)32]Br. The IR spectra are discussed. 相似文献
Reaction of [(η-C7H7)Mo(CO)3][PF6] and [(η-C5H5)Fe(CO)2CH3CN][PF6] with ditertiary phosphine ligands afforded products of three types; the monosubstituted complexes [(Ring)M(CO)2Ph2P(CH2)nPPh2][PF6] (Ring = η-C7H7, M = Mo, N = 1; Ring = η-C5H5, M = Fe, N = 1 and 2), the chelated complexes [(Ring)M(CO)Ph2P(CH2)nPPh2][PF6] (Ring = η-C7H7, M = Mo, N = 1 and 2; Ring = η-C5H5, M = Fe, N = 1 and 2), and the dinuclear complex [{(η-C7H7)Mo(CO)2}2 -μ- Ph2PCH2CH2PPh2][(PF6)2]. Spectroscopic properties, including 31P NMR, are reported. 相似文献
The reactions of the cationic complexes [CpMn(CO)2NO]+, [MeCpMn(CO)2NO]+ (Cp = η5-C5H5, MeCp = η5-C5H4CH3), [CpRe(CO)2NO]+, [CpMn(CO)(L)NO]+ (L = PPh3, PEt2Ph, AsPh3, CNMe, CNEt), {[CpMn(CO)NO]2Me2PC2H4PMe2}2+ and {CpMn(CO)NO]2Ph2PC2H4PPh2}2+ with liquid NH3 yield the neutral carbamoyl complexes CpMn(CO)(NO)CONH2, MeCpMn(CO)(NO)CONH2, CpRe(CO)(NO)CONH2, CpMn(L)(NO)CONH2 (L = PPh3, PEt2Ph, AsPh3, CNMe, CNEt), [CpMn(NO)CONH2]2Me2PC2H4PMe2 and [CpMn(NO)CONH2]2Ph2PC2H4PPh2. Properties and reactions of these new compounds are described. 相似文献
Complexes of the type {Fp′(solvent)}+ PF6?, 3a–3d, (Fp′ = (η -C5Me5)Fe(CO)2, solvent = THF, CH3COCH3, CH3CN, or pyridine) are conveniently prepared by the reaction between Fp′2 and Cp2Fe+ PF6 (Cp = η5-C5H5) in the solvent under ambient conditions. The complexes {Fp′L}+ PF6?, 3e–3g, (L = CO, PPh3, P(OPh)3) are readily prepared from {Fp′THF}+. Fp′H is formed by treatment of 3a with NaBH4. Fp′SC(S)NMe2 can be prepared from 3a or 3e and NaSC(S)NMe2. 相似文献
The use of ferricenium cations [(C5H5)2FE]X (X = BF4, PF6, SbF6) as one-electron oxidizing agents for organometallic complexes is demonstrated. Sandwich compounds M(C5H5)2 (M = Cr, Co, Ni) and Cr(C6H6)2 are oxidized in nearly quantitative yield to the corresponding cations [M(C5H5)2]BF4 and [(C6H6)2Cr]BF4. The metalmetal bond in the dinuclear organometallic complexes [DienylM(CO)n]2 (M = Mo (n = 3), Fe (n = 2), Ni (n = 1)) and Co2(CO)8 is fissioned by (C5H5)2Fe+ in the presence of neutral ligands L to form the corresponding cationic compounds [DienylM(CO)nLm]X (M = Mo (n = 2), Fe (n = 2), Ni (n = 0)) and [Co(CO)3L2BF4 (L = VB and VIB donor ligands) in high yields.The practical applications of ferricenium cations are discussed in comparison with other methods for the preparation of cationic organometallic complexes. 相似文献
Preparation, Mössbauer and Vibrational Spectra of the Complexes [SnCl4F]?, [SnCl4(NCS)]?, and [SnCl4(NCS)2]2? N(CH2)4F and N(CH2)4SCN react in liquid SO2 with SnCl4 yielding the adducts [N(CH3)4][SnCl4F] (I), [N(CH3)4][SnCl4(NCS)] (II) and [N(CH3)4]2[SnCl4(NCS)2] (III).respectively. Mössbauer and vibrational spectra indicate for the anion of I a fluoro-bridged species, which is probably tetrameric like the isoelectronic SbCl4F. For II dimeric moieties are proposed with bridging S-atoms, while [SnCl4(NCS)2]2? has an octahedral structure with N-bonded isothiocyanate groups in the trans-positions. 相似文献
The reaction between InCl and [Mo2(CO)6(η-C5H5)2] affords [InCl&{;Mo(CO)3(η-C5H5)&};], 6a which has been characterised as a THF adduct [InCl(THF)&{;Mo(CO)3(η-C5H5)&};2], 10, by X-ray crystallography. An additional complex, [InCl2&{;Mo(CO)3(η-C5H5)&};2]−, 11, is also formed in this reaction. Similar products are reported for reactions involving [M2(CO)6(η-C5H5)2] (M = Cr, W). The reaction between InCl and [Fe2(CO)4(η-C5H5)2] affords [InCl{Fe(CO)2(η-C5H5)}2], 17, and [InCl2{Fe(CO)2(η-C5H5)}], whilst that between InI and [Fe2(CO)4(η-C5H5)2] affords [InI{Fe(CO)2(η-C5H5)}2], 19. 相似文献
B3N3Me6Cr(CO)3 reacts with [AsPh4] [SnCl3] and [AsPh4] [GeCl3] in tetrahydrofuran to give [AsPh4]3[Cr(CO)3(SnCl3)3] and [AsPh4]3[Cr(CO)3(GeCl3)3], respectively. According to IR. and 13C-NMR.-data, the tricarbonylate anions possess a meridional configuration. The donor-acceptor properties of SnCl3? and GeCl3? in the anions [Cr(CO)3(ECl3)3]3? (E = Sn, Ge) are very similar. A similar synthesis of [AsPh4]3[Cr(CO)3(SnF3)3] was not successful. 相似文献
Metal Complexes of Biologically Important Ligands. CXVII [1] Addition of the O'Donnell Reagent [Ph2C=NCHCO2Me]– to Coordinated, Unsaturated Hydrocarbons of [(C6H7)Fe(CO)3]+, [C7H9Fe(CO)3]+, [(C7H7)M(CO)3]+ (M = Cr, Mo), and [(C2H4)Re(CO)5]+. α-Amino Acids with Organometallic Side Chains The addition of [Ph2C=NCHCO2Me]– to [(C6H7)Fe(CO)3]+, [(C7H9)Fe(CO)3]+, [(C7H7)M(CO)3]+ (M = Cr, Mo) and [(C2H4)Re(CO)5]+ gives derivatives of α-amino acids with organometallic side chains. The structure of [(η4-C6H7)CH(N=CPh2)CO2Me]Fe(CO)3 was determined by X-ray diffraction. From the adduct of [Ph2C=NCHCO2Me]– and [(C7H7)Mo(CO)3]+ the Schiff base of a new unnatural α-amino acid, Ph2C=NCH(C7H7)CO2Me, was obtained. 相似文献
1,1,3,3-Tetrakis(dimethylamino)-1λ5,3λ5-diphosphete as Ligand in Coordination Compounds 1,1,3,3-Tetrakis(dimethylamino)-1λ5,3λ5-diphosphete, 1 , reacts with GeCl2 · 1,4-dioxane, SnCl2, and (CO)5W(Z-cyclooctene) to give the complexes {HCP[N(CH3)2]2}2 · GeCl2, 3 , {HCP[N(CH3)2]2}2 · SnCl2, 4 , and {HCP[N(CH3)2]2}2 · W(CO)5, 5 , respectively. The n.m.r., mass, and i.r. spectra of the new compounds as well as the crystal and molecular structures of 3 and 4 are reported and the bonding situation in compounds 3–5 is discussed. 相似文献
Reaction of platinum(IV) chloride with SnCl2?·?2H2O in the presence of [NHR3]3Cl (R?=?Me, Et) in 3M hydrochloric acid affords the anionic five-coordinate platinum(II) complexes [NHR3]3[Pt(SnCl3)5], R?=?Me (1), Et (2), respectively. Moreover, platinum(IV) chloride reacts with SnCl2?·?2H2O in the presence of bis(triphenylphosphoranylidene)ammonium chloride in acetone/dichloromethane to form [N(PPh3)2]3[Pt(SnCl3)5] (3). In contrast, reaction of an acetone solution of platinum(IV) chloride with SnCl2?·?2H2O in the presence of bis(triphenylphosphoranylidene) ammonium chloride resulted in the formation of cis-[N(PPh3)2]2[PtCl2(SnCl3)2] (4). The same products are obtained by using a platinum(II) salt as starting material. Similarly, cis and trans- dichlorobis(diethyl sulfide)platinum(II) reacts with SnCl2?·?2H2O in 5M hydrochloric acid to give [PtCl(SEt2)3]3[Pt(SnCl3)5] (5) by facile insertion of SnCl2 into the Pt–Cl bond. However, treatment of an acetone solution of cis- and trans-[PtCl2(SEt2)2] with SnCl2?·?2H2O in the presence of a small amount of HCl resulted in the formation of 5, which dissociates in solution to give [PtCl2(SEt2)2]. The complexes have been fully characterized by elemental analysis and multinuclear NMR (1H,?13C,?195Pt,?119Sn) spectroscopy. A structure determination of crystals grown from a solution of 2 by X-ray diffraction methods shows that platinum adopts a regular trigonal bipyramidal geometry. 相似文献
Nitriles react with PF5 and also with AsF5, SbF5 forming 1:1-adducts. Using C2Cl3F3 as a solvent is of advantage for this reaction. PF5·CH3CN and [N(C2H5)4]SH give [N(C2H5)4][P2S2F8] with a sulfur double bridge and hexafluorophosphate in acetonitrile [1]. In case of AsF5·CH3CN a salt with the anion [AsF5NHCSCH3]? has been isolated [2]. Following products have been confirmed in a reaction mixture of PF5·CH3CN and SH? in acetonitrile by NMR (31P and 19F): [PF6]?, [F5PSPF5]2?, , F4PSH, F3PS, HPS2F2, [PS2F2]?, [F5PNC(SH)CH3]?, [F5PNHCSCH3]?, [F5PSH]?. With a ratio PF5·CH3CN: SH? = 2:1 the S-bridge-complexes are prefered whereas in case of a ratio 1:1 the non-bridged P-complexes are the main products. 相似文献
Reactions of reactive cyclopentadienyliron complexes C5H5Fe(CO)2I, [C5H5Fe(CO)2THF]BF4, [C5H5Fe(CO)((CH3)2S)2]BF4 and [C5H5Fe(p-(CH3)2C6H4)]PF6 with P(OR)3 as ligands (R = CH3, C2H5, i-C3H7 and C6H5) lead to the formation of the complex compounds C5H5Fe(CO)2?n(P(OR)3)nI and [C5H5Fe(CO)3?n(P(OR)3)n]X (n = 1, 2 and n = 1–3, X = BF4, PF6). Spectroscopic investigations (IR, 1H, 13C and 31P NMR) indicate an increase of electron density on the central metal with increasing substitution of CO groups by P(OR)3 ligands. The stability of the compounds increase in the same way. 相似文献
Complexes of the Alkali Metal Tetraphenylborates with Macrocyclic Crown Ethers Alkali metal tetraphenylborates, MB(C6H5)4 (M = Li to Cs), react in tetrahydrofuran with macrocyclic crown ethers to give complexes of the general formula MB(C6H5)4(crown)m(THF)n. Suitable single crystals for X‐ray structure analysis were grown from a solvent mixture of tetrahydrofuran and n‐hexane. The salt like complexes [Li(12‐crown‐4)(thf)][B(C6H5)4] ( 1 ), [Na(15‐crown‐5)(thf)][B(C6H5)4] ( 2 ), and [Cs(18‐crown‐6)2][B(C6H5)4] · THF ( 6 ), the mononuclear molecular complexes [KB(C6H5)4(18‐crown‐6)(thf)] ( 3 ), [RbB(C6H5)4(18‐crown‐6)] ( 4 ), and [CsB(C6H5)4(18‐crown‐6)] · THF ( 5 ), and the compound [CsB(C6H5)4(18‐crown‐6)]2[Cs(18‐crown‐6)2][B(C6H5)4] ( 7 ), which contains a binuclear molecule ([CsB(C6H5)4(18‐crown‐6)]2) beside a [Cs(18‐crown‐6)2]+ cation and a [B(C6H5)4]? anion, are described. All compounds are charactarized by infrared spectra, elemental analysis, NMR‐spectroscopy, and X‐ray single crystal structure analysis. 相似文献
