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1.
Transition Metal Phosphido Complexes. XI. Diphosphene Complexes of the Type (R3P)2Ni[η2-(PR′)2] and Phosphido-Bridged Nickel(I) Complexes of the Type [R3PNiP(SiMe3)2]2(Ni? Ni) From reactions of complexes of the type (R3P)2NiCl2 1 (R = Me a , Et b , nBu c , iBu d , Ph e , iPr f , Cy g ) with LiP(SiMe3)2 in a 1:2 molar ratio the diphosphene complexes (R3P)2Ni[η2-(PSiMe3)2] 4a–c and the phosphido-bridged nickel(I) complexes [R3PNiP(SiMe3)2]2 (Ni? Ni) 7a–g are available. Using low temperature n.m.r. measurements the monosubstitution products (R3P)2NiClP(SiMe3)2 2a–c and the nickel(0) diphosphane complexes R3PNi[η1-P2(SiMe3)4] 6a–g can be detected as intermediates. In reactions in a 1:1 molar ratio the formation of the diphosphorus complexes [(R3P)2Ni]2P2 9b, 9c is n.m.r. spectroscopically detectable. 1b reacts with LiP(SiMe3)CMe3 to give first the nickel(0) diphosphane complex Et3PNi[η1-P(SiMe3)CMe3? P(SiMe3)CMe3] 10 , which can be isolated at low temperatures, finally yielding (Et3P)2Ni[η2-(PCMe3)2] 11 and [Et3PNiP(SiMe3)CMe3]2 (Ni? Ni) 12. 11 as well as (Et3P)2Ni[η2-(PPh)2] 14 can also be obtained reacting 1b with R′P(SiMe3)2 (R′ = CMe3, Ph). The best yields of diphosphene complexes result from [2+1] cyclocondensation reactions of 1a–c with P2(SiMe3)4 to give 4a–c and of 1b with [P(SiMe3)CMe3]2 to give 11 . N.m.r. and mass spectral data are reported. 相似文献
2.
Transition Metal Phosphido Complexes. XII. Diphosphene Complexes (DRPE)Ni[η2-(PR′)2] and the Structure of (DCPE) NiP (SiMe3)2 LiP(SiMe3)2 reacts with the complexes (DRPE)NiCl2 1 (DRPE = R2PCH2CH2PR2; R = Et: DEPE a ; R = Cy: DCPE b ; R = Ph: DPPE c ) to form the diphosphene complexes (DRPE)Ni[η2-(PSiMe3)2] 5a–c . Using low temperature nmr measurements the monosubstitution products (DRPE)Ni[P(SiMe3)2]Cl 2a–c and the disubstitution products (DRPE)Ni[P(SiMe3)2]2 3a, 3c can be detected as intermediates. From the reaction of 1b the paramagnetic nickel(I) complex (DCPE)NiP(SiMe3)2 4b can be isolated. Reacting 1a, 1b with LiP(SiMe3)CMe3 the complexes (DRPE)Ni[P(SiMe3)CMe3]Cl 8a, 8b , which are analogous to 2 , and the nickel(0) diphosphine complex (DEPE)Ni[η1-P(SiMe3)CMe3P(SiMe3)CMe3] 9a can be detected n.m.r. spectroscopically, but no diphosphene complexes can finally be isolated. The diphosphene complexes (DRPE)Ni[η2(PPh)2] 10a-c are available from reactions of PhP(SiMe3)2with l a - c. MeP(SiMe,), reacts only with 1b to give a diphosphene complex (DCPE)Ni[η2(PMe)2] 11 b. Reacting [P(SiMe3)CMe3]2 with 1a-c the diphosphene complexes (DRPE)Ni[η2(PCMe3)2] 12a-c can be obtained. 4b crystallizes monoclinic in the space group P2Jc with a = 1228.6 pm, b = 2387.1 pm, c = 2621.8 pm, β = 92.16°, and Z = 8 formula units. The nickel atom is nearly planar coordinated by three phosphorus- atoms, the phosphorus atom of the terminal P(SiMe3)2 group is pyramidally coordinated. The Ni? P bond distances of the two four-coordinated phosphorus atoms are with 219.2 pm and 220.2 pm only slightly shorter than the corresponding distance of the P-atom of the P(SiMe3)2 group with 223.5 pm. N.m.r. and mass spectral data are reported. 相似文献
3.
Harald Krautscheid Eberhard Matern Jolanta Olkowska‐Oetzel Jerzy Pikies Gerhard Fritz 《无机化学与普通化学杂志》2001,627(4):675-678
Coordination Chemistry of P‐rich Phosphanes and Silylphosphanes. XXII. The Formation of [η2‐{tBu–P=P–SiMe3}Pt(PR3)2] from (Me3Si)tBuP–P=P(Me)tBu2 and [η2‐{C2H4}Pt(PR3)2] (Me3Si)tBuP–P = P(Me)tBu2 reacts with [η2‐{C2H4}Pt(PR3)2] yielding [η2‐{tBu–P=P–SiMe3}Pt(PR3)2]. However, there is no indication for an isomer which would be the analogue to the well known [η2‐{tBu2P–P}Pt(PPh3)2]. The syntheses and NMR data of [η2‐{tBu–P=P–SiMe3}Pt(PPh3)2] and [η2‐{tBu–P=P–SiMe3}Pt(PMe3)2] as well as the results of the single crystal structure determination of [η2‐{tBu–P=P–SiMe3}Pt(PPh3)2] are reported. 相似文献
4.
Transition Metal Phosphido Complexes. XV. (DRPE)Ni-Complexes with PH-Containing, η2-Coordinated Diphosphene Ligands and the Diphosphorus Complexes [(DRPE)Ni]2P2 The complexes (DRPE)NiCl2 1 (DRPE = R2PCH2CH2PR2; R = Et: DEPE a ; R = Cy: DCPE b ; R = Ph: DPPE c ) react with the silylphosphines (Me3Si)3P, (Me3Si)2PH, Me3SiPH2 and [(Me3Si)2P]2 to form the diphosphorus complexes [(DRPE)Ni]2P2 3a–c and the nickel(0) complexes (DRPE)2Ni 4a–c . In the reaction of 1b with Me3SiPH2 the P2H2 complex (DCPE)Ni[η2-(PH)2] 5b can be isolated at low temperature as an intermediate. Cleaving the Si? P bonds in (DRPE)Ni[η2-(PSiMe3)2] 2a, 2b with CH3OH gives also the P2 complexes 3a, 3b . Intermediates containing HP=PSiMe3 and P2H2 as ligands can be detected nmr spectroscopically. Reacting 1a–c with (Me3Si)2PP(SiMe3)CMe3 the complexes (DRPE)Ni(η2-Me3SiP?PCMe3) 7a–c containing asymmetric diphosphene ligands can be obtained. 7a reacts with CH3OH yielding the P2 complex 3a directly, while 7b with CH3OH first gives (DCPE)Ni(η2-HP?PCMe3) 8b . In solution 8b can be transformed into 3b upon heating to 80°C. N.m.r. and mass spectral data are reported. 相似文献
5.
S. Chitsaz H. Folkerts J. Grebe T. Grb K. Harms W. Hiller M. Krieger W. Massa J. Merle M. Mhlen B. Neumüller K. Dehnicke 《无机化学与普通化学杂志》2000,626(3):775-783
Crystal Structures of a Series of Compounds with Cations of the Type [R3PNH2]+, [R3PN(H)SiMe3]+, and [R3PN(SiMe3)2]+ The crystal structures of a series of compounds with cations of the type [R3PNH2]+, [R3PN(H)SiMe3]+, and [R3PN(SiMe3)2]+, in which R represents various organic residues, are determined by means of X‐ray structure analyses at single crystals. The disilylated compounds [Me3PN(SiMe3)2]+I–, [Et3PN(SiMe3)2]+I–, and [Ph3PN(SiMe3)2]+I3– are prepared from the corresponding silylated phosphaneimines R3PNSiMe3 with Me3SiI. [Me3PNH2]Cl (1): Space group P21/n, Z = 4, lattice dimensions at –71 °C: a = 686.6(1), b = 938.8(1), c = 1124.3(1) pm; β = 103.31(1)°; R = 0.0239. [Et3PNH2]Cl (2): Space group Pbca, Z = 8, lattice dimensions at –50 °C: a = 1272.0(2), b = 1147.2(2), c = 1302.0(3) pm; R = 0.0419. [Et3PNH2]I (3): Space group P212121, Z = 4, lattice dimensions at –50 °C: a = 712.1(1), b = 1233.3(2), c = 1257.1(2) pm; R = 0.0576. [Et3PNH2]2[B10H10] (4): Space group P21/n, Z = 4, lattice dimensions at –50 °C: a = 809.3(1), b = 1703.6(1), c = 1800.1(1) pm; β = 96.34(1)°; R = 0.0533. [Ph3PNH2]ICl2 (5): Space group P1, Z = 2, lattice dimensions at –60 °C: a = 825.3(3), b = 1086.4(3), c = 1241.2(4) pm; α = 114.12(2)°, β = 104.50(2)°, γ = 93.21(2)°; R = 0.0644. In the compounds 1–5 the cations are connected with their anions via hydrogen bonds of the NH2 groups with 1–3 forming zigzag chains. [Me3PN(H)SiMe3][O3S–CF3] (6): Space group P21/c, Z = 8, lattice dimensions at –83 °C: a = 1777.1(1), b = 1173.6(1), c = 1611.4(1) pm; β = 115.389(6)°; R = 0.0332. [Et3PN(H)SiMe3]I (7): Space group P21/n, Z = 4, lattice dimensions at –70 °C: a = 1360.2(1), b = 874.2(1), c = 1462.1(1) pm; β = 115.19(1)°; R = 0.066. In 6 and 7 the cations form ion pairs with their anions via NH … X hydrogen bonds. [Me3PN(SiMe3)2]I (8): Space group P21/c, Z = 8, lattice dimensions at –60 °C: a = 1925.4(9), b = 1269.1(1), c = 1507.3(4); β = 111.79(3)°; R = 0.0581. [Et3PN(SiMe3)2]I (9): Space group Pbcn, Z = 8, lattice dimensions at –50 °C: a = 2554.0(2), b = 1322.3(1), c = 1165.3(2) pm; R = 0.037. [Ph3PN(SiMe3)2]I3 (10): Space group P21, Z = 2, lattice dimensions at –50 °C: a = 947.7(1), b = 1047.6(1), c = 1601.6(4) pm; β = 105.96(1)°; R = 0.0334. 8 to 10 are built up from separated ions. 相似文献
6.
Metal Complexes of Biologically Important Ligands. CIII. [1] Palladium(II), Platinum(II), Ruthenium(II), Rhodium(III), and Iridium(III) Complexes of Desoxyfructosazine The reactions of the pyrazine derivative desoxyfructosazin(pz) with K2PtCl4 and with the chlorobridged [M(PR3)Cl2]2 (M = Pd, Pt), [(η5-C5Me5)MCl2]2 and [(η6-p-Cymol)RuCl2]2 give the watersoluble complexes cis-Cl2Pt(pz)2, (R3P)(Cl)M(pz)M(Cl)(PR3) (M = Pd, Pt), (η5-C5Me5)(Cl)2M(pz)M(Cl)2(η5-C5Me5) (M = Rh, Ir), (η6-p-Cymol)(Cl2)Ru(pz)Ru(Cl)2(η6-p-Cymol). 相似文献
7.
On the Reactivity of (η5-C5Me5)(CO)2FeP(SiMe3)2 Toward P-Chloromethylene phosphanes The reaction of (η5-C5Me5)(CO)2FeP(SiMe3)2 ( 2 ) with three equivalents of Cl? P?C(SiMe3)2 ( 3a ) afforded the 3-methanediyl-1,3,5,6-tetraphosphabicyclo[3.1.0]hex-2-ene (η5-C5Me5)(CO)2Fe? ( 6a ). In contrast, 2 reacts with two equivalents of Cl? P?C(Ph)SiMe3 ( 3b ) to give the thermolabile (η5-C5Me5) · (CO)2Fe? P[P?C(Ph)SiMe3]2 ( 4b ) which decomposed during the reaction with further 3b. 4 b was also obtained from (η5-C5Me5)(CO)2Fe? P(SiMe3)? P?C(SiMe3)2 ( 1a ) and two equivalents of 3b . 相似文献
8.
Substituted phosphines of the type Ph2PCH(R)PPh2 and their PtII complexes [PtX2{Ph2PCH(R)PPh2}] (R = Me, Ph or SiMe3; X = halide) were prepared. Treatment of [PtCl2(NCBut)2] with Ph2PCH(SiMe3)-PPh2 gave [PtCl2(Ph2PCH2PPh2)], while treatment with Ph2PCH(Ph)PPh2 gave [Pt{Ph2PCH(Ph)PPh2}2]Cl2. Reaction of p-MeC6H4C≡CLi or PhC≡CLi with [PtX2{Ph2PCH(Me)PPh2}] gave [Pt(C≡CC6H4Me-p)2-{Ph2PCH(Me)PPh2}] (X = I) and [Pt{Ph2PC(Me)PPh2}2](X = Cl),while reaction of p-MeC6H4C≡CLi with [Pt{Ph2PCH(Ph)PPh2}2]Cl2 gave [Pt{Ph2PC(Ph)PPh2}2]. The platinum complexes [PtMe2(dpmMe)] or [Pt(CH2)4(dpmMe)] fail to undergo ring-opening on treatment with one equivalent of dpmMe [dpmMe = Ph2PCH(Me)PPh2]. Treatment of [Ir(CO)Cl(PPh3)2] with two equivalents of dpmMe gave [Ir(CO)(dpmMe)2]Cl. The PF6 salt was also prepared. Treatment of [Ir(CO)(dpmMe)2]Cl with [Cu(C≡CPh)2], [AgCl(PPh3)] or [AuCl(PPh3)] failed to give heterobimetallic complexes. Attempts to prepare the dinuclear rhodium complex [Rh2(CO)3(μ-Cl)(dpmMe)2]BPh4 using a procedure similar to that employed for an analogous dpm (dpm = Ph2PCH2PPh2) complex were unsuccessful. Instead, the mononuclear complex [Rh(CO)(dpmMe)2]BPh4 was obtained. The corresponding chloride and PF6 salts were also prepared. Attempts to prepare [Rh(CO)(dpmMe)2]Cl in CHCl3 gave [RhHCl(dpmMe)2]Cl. Recrystallization of [Rh(CO)(dpmMe)2]BPh4 from CHCl3/EtOH gave [RhO2(dpmMe)2]BPh4. Treatment of [Rh(CO)2Cl2]2 with one equivalent of dpmMe per Rh atom gave two compounds, [Rh(CO)(dpmMe)2]Cl and a dinuclear complex that undergoes exchange at room temperature between two formulae: [Rh2(CO)2(μ-Cl)(μ-CO)(dpmMe)2]Cl and [Rh2(CO)2-(μ-Cl)(dpmMe)2]Cl.
This revised version was published online in June 2006 with corrections to the Cover Date. 相似文献
9.
Preparation and Reactivity of Platinumcyclobutadiene Complexes [PtCl2(C4R4)L] H[PtCl3(C4H8)], prepared by reduction of H2[PtCl6] with n-butanol reacts with 2-pentyne to give equal amounts of the regioisomers [PtCl2(C4Et2Me2)] ( 3 a, 3 b ). An equimolar mixture of 2-butyne/3-hexyne reacts under the same conditions to give [PtCl2(C4Me4)] ( 1 ), [PtCl2(C4Et4)] ( 2 ) and [PtCl2(C4Et2Me2)] ( 3 a ) in a molar ratio 1:1.3:6.6. 1 and 2 react with ligands L (L = py a , p-tol b , PPh3 c , AsPh3 d , SbPh3 e ) to give complexes of the type [PtCl2(C4R4)L]. The complexes were characterized by microanalysis as well as by i.r., 1H- and 13C-n.m.r. spectroscopy. 相似文献
10.
Coordination Chemistry of P‐rich Phosphanes and Silylphosphanes XXI The Influence of the PR3 Ligands on Formation and Properties of the Phosphinophosphinidene Complexes [{η2‐tBu2P–P}Pt(PR3)2] and [{η2‐tBu2P1–P2}Pt(P3R3)(P4R′3)] (R3P)2PtCl2 and C2H4 yield the compounds [{η2‐C2H4}Pt(PR3)2] (PR3 = PMe3, PEt3, PPhEt2, PPh2Et, PPh2Me, PPh2iPr, PPh2tBu and P(p‐Tol)3); which react with tBu2P–P=PMetBu2 to give the phosphinophosphinidene complexes [{η2‐tBu2P–P}Pt(PMe3)2], [{η2‐tBu2P–P}Pt(PEt3)2], [{η2‐tBu2P–P}Pt(PPhEt2)2], [{η2‐tBu2P–P}Pt(PPh2Et)2], [{η2‐tBu2P–P}Pt(PPh2Me)2], [{η2‐tBu2P–P}Pt(PPh2iPr], [{η2‐tBu2P–P}Pt(PPh2tBu)2] and [{η2‐tBu2P–P}Pt(P(p‐Tol)3)2]. [{η2‐tBu2P–P}Pt(PPh3)2] reacts with PMe3 and PEt3 as well as with tBu2PMe, PiPr3 and P(c‐Hex)3 by substituting one PPh3 ligand to give [{η2‐tBu2P1–P2}Pt(P3Me3)(P4Ph3)], [{η2‐tBu2P1–P2}Pt(P3Ph3)(P4Me3)], [{η2‐tBu2P1–P2}Pt(P3Et3)(P4Ph3)], [{η2‐tBu2P1–P2}Pt(P3MetBu2)(P4Ph3)], [{η2‐tBu2P1–P2}Pt(P3iPr3)(P4Ph3)] and [{η2‐tBu2P1–P2}Pt(P3(c‐Hex)3)(P4Ph3)]. With tBu2PMe, [{η2‐tBu2P–P}Pt(P(p‐Tol)3)2] forms [{η2‐tBu2P1–P2}Pt(P3MetBu2)(P4(p‐Tol)3)]. The NMR data of the compounds are given and discussed with respect to the influence of the PR3 ligands. 相似文献
11.
Heterobimetallic complexes such as [η-areneMCl(SPPh2)2Pt(S2CNEt2)] (I, M = Ru, Os) and [η-C5Me5RhCl(SPPh2)2Pt(S2CNEt2)] (II) have been synthesised by reaction of NEt2H2[Pt(S2CNEt2)(Ph2PS)2] with either [M(η-arene)Cl2]2 or [Rh(η-C5Me5)Cl2]2 (2/1) molar ratio). Further reactions of I include facile chloride displacement with a range of neutral ligands L to give [η-areneML(SPPh2)2Pt(S2CNEt2)+ (III) cations and formation of tri- and penta-metallic species on treatment with more [Pt(S2CNEt2)(Ph2PS)2]?. 相似文献
12.
《Journal of organometallic chemistry》1994,481(2):195-204
The reaction of K2[PtCl4] with 2-(1-methylbenzyl)pyridine, HL, and 2-benzylpyridine, HL', affords the cyclometallated species [{Pt(L)Cl}2] (1) and [{Pt(L')Cl}2] (2), respectively. The chloride bridge in complex 1 can be split by neutral or anionic species to give the monomeric, [Pt(L)(Ph3P)Cl], as two isomers, trans-P-Pt-C (3) and trans-P-Pt-N, (4), [Pt(L)(py)Cl] (5), [Pt(L)(CO)Cl] (6), [Pt(L)(CNCH2SO2C6H4CH3-4)Cl] (7), [Pt(L)(acac)] (Hacac = 2,4-pentanedione) (8), [Pt(L)(dppm)][BF4] (dppm = bis(diphenyl-phosphino)methane) (9), [Pt(L)(dppe)][BF4] (dppe = bis(diphenylphosphino)ethane) (10) and [Pt(L)(dipy)][BF4](dipy = 2,2'-dipyridine) (11). Similarly, compound 2, by reaction with Ph3P, affords [Pt(L')(Ph3P)Cl], as two isomers, trans-P-Pt-C (12) and trans-P-Pt-N (13). Reaction of compounds 1 or 4 with AgBF4 in acetonitrile affords [Pt(L)(CH3CN)2IBF4] (14) or [Pt(L)(Ph3P)-(CH3CN)][BF4] (15). From these, [Pt(L)(Ph3P)2][BF4] (16), [Pt(L)(Ph3P)(CO)][BF4] (17) and [Pt(L)(Ph3P)(py)][BF4] (18), can be obtained by displacement of the coordinated acetonitrile. The new complexes were characterized by IR, 1H and 31P NMR and FAB-MS spectroscopic techniques. The NMR spectra at room temperature of most of the species derived from HL give evidence for the presence in solution of two diastereomers a and b. The structure of one diastereomer of complex 4 has been solved by single crystal X-ray diffraction, 4b. The platinum atom is in an almost square planar geometry with a P-Pt-N trans arrangement: Pt-N = 2.095(3), Pt-C = 1.998(4), Pt-P = 2.226(1) and Pt-Cl = 2.400(1) Å. The six-membered cyclometallated ring is in a boat conformation, with the CH3 group in an equatorial position, i.e pointing away from the metal. Attempts to obtain [{Pt(L″)Cl}2] (HL″ = 2-(dimethylbenzyl)pyridine), afforded an insoluble product heavily contaminated by platinum metal; treatment of this crude material with Ph3P gave [Pt(L″)(Ph3P)Cl] (19). 相似文献
13.
Formation and Structure of the Cyclophosphanes P4(CMe3)2[P(CMe3)2]2 and P4(SiMe3)2[P(CMe3)2]2 n-Triphosphanes showing a SiMe3 and a Cl substituent at the atoms P1 and P2, like (Me3C)2P? P(SiMe3)? P(CMe3)Cl 3 or (Me3C)2P? P(Cl)? P(SiMe3)2 4 are stable only at temperatures below ?30°C. Above this temperature these compounds lose Me3SiCl, thus forming cyclotetraphosphanes, P4(CMe3)2[P(CMe3)2]2 1 out of 3 , P4(SiMe3)2[P(SiMe3)2]2 2a (cis) and 2b (trans) out of 4 . The formation of 1 proceeds via (Me3C)2P? P?PCMe3 5 as intermediate compound, which after addition to cyclopentadiene to give the Diels-Alder-adduct 6 (exo and endo isomers) was isolated. 6 generates 5 , which then forms the dimer compound 1 . Likewise (Me3C)2P? P?P-SiMe3 8 (as proven by the adduct 7 ) is formed out of 4 , leading to 2a (cis) and 2b (trans). Compound 1 is also formed out of the iso-tetraphosphane P[P(CMe3)2]2[P(CMe3)Cl] 9 , which loses P(CMe3)2Cl when warmed to a temperature of 20°C. 1 crystallizes monoclinically in the space group P21/a (no. 14); a = 1762.0(15) pm; b = 1687.2(18) pm; c = 1170.5(9) pm; β = 109.18(5)° and Z = 4 formula units in the elementary cell. The molecule possesses E conformation. The central four-membered ring is puckered (approx. symmetry 4 2m; dihedral angle 47.4°), thus bringing the substituents into a quasi equatorial position and the nonbonding electron pairs into a quasi axial position. The bond lengths in the four-membered ring of 1 (d (P? P) = 222.9 pm) are only slightly longer than the exocyclic bonds (221.8 pm). The endocyclic bond angles \documentclass{article}\pagestyle{empty}\begin{document}$ \bar \beta $\end{document}(P/P/P) are 85.0°, the torsion angles are ±33° and d (P? C) = 189.7 pm. 相似文献
14.
Hans J. Breunig Tim Koehne Ana Maria Preda Cristian Silvestru Luis F. Piedra-Garza 《Journal of organometallic chemistry》2010,695(9):1307-1313
The syntheses and spectroscopic (NMR, MS) investigations of the antimonates [Ph4P]+[Me2SbCl4]− (1), [Me4Sb]+[Me2SbCl4]− (2), [Et4N]+[Ph2SbCl4]− (3), [Bu4N]+[Ph2SbCl4]− (4), [Me4Sb]+[Ph2SbCl4]− (5), [Et3MeSb]+[Ph2SbCl4]− (6), [Et4N]+[Ph2SbF4]− (7) and [Et4N]+[Ph2SbBr4]− (8) are reported. Halogen scrambling reactions of Et4NBr or Ph4EBr (E = P, Sb) with R2SbCl3 (R = Me, Ph) produce mixtures of compounds from which crystals of [Et4N]+[Ph2SbBr1.24Cl2.76]− (9), [Et4N]+[Ph2SbBr2.92Cl1.08]− (10) or [Ph4Sb]+[Me2SbCl4]− (11) were isolated. The crystal and molecular structures of 1 and 3-11 are reported. 相似文献
15.
Dmitry A. Loginov 《Journal of organometallic chemistry》2009,694(2):157-12442
Complex Cp∗PtCl2 (Cp∗ = η-C4Me4) reacts with the carborane anions [7,8-C2B9H11]2− and [9-SMe2-7,8-C2B9H10]− giving platinacarboranes Cp∗Pt(η-7,8-C2B9H11) (1) and [Cp∗Pt(η-9-SMe2-7,8-C2B9H10)]+ (2), respectively. Reactions of the [Cp∗Pt]2+ fragment (as a labile nitromethane solvate) with the sandwich compounds Cp∗Fe(η-C5H3Me2BMe) and Cp∗Rh(η5-C4H4BPh) afford the triple-decker cations [Cp∗Pt(μ-η:η-C5H3Me2BMe)FeCp∗]2+ (3) and [Cp∗Pt(μ-η5:η5-C4H4BPh)RhCp∗]2+ (4) with bridging boratabenzene and borole ligands. The structures of 1 and 3(CF3SO3)2 were determined by X-ray diffraction. 相似文献
16.
Kim D. Janda Wesley W. McConnell Gregory O. Nelson Michael E. Wright 《Journal of organometallic chemistry》1983,259(2):139-143
A new metal-metal bonded binuclear iron system [Me2SiCH2CH2SiMe2][η5-C5H4Fe(CO)2]2 (2) has been prepared by treating two equivalents of NaCp with one equivalent of ClSi(Me)2CH2CH2SiClMe2 obtaining the intermediate (C5H5)Si(Me)2CH2CH2Si(Me)2(C5H5) which then is directly allowed to react with Fe(CO)5 given 2 in 30% yield. From this cyclopentadienyldisilyl linked system three new binuclear irom complexes are formed. Treatment of 2 with Na/Hg in THF produced the dianion [Me2SiCH2CH2SiMe2][η5-C5H4Fe(CO)2?]2 which is quenched with CH3I giving [Me2SiCH2CH2SiMe2][η5-C4H4Fe(CO)2CH3]2 (4) in 76% yield. Complex 2 is oxidized with 1.2 equivalent of I2 to give [Me2SiCH2CH2SiMe2][η5-C5H4Fe(CO)2I]2 (5) in 85% yield. Photolysis of 5 (1 equiv.) and PPh3 (3 equiv.) results in the formation of the bis-substituted compound [Me2SiCH2CH2SiMe2][η5-C5H4Fe(CO)(PPh3)I]2 (6). These four new binuclear iron complexes are characterized by 1H, 13C, and 31P NMR and IR spectroscopy. 相似文献
17.
1,2-Diphosphaferrocenes as Ligands in Transition Metal Complexes. X-Ray Structure Analysis of [(η5-1,3-tBu2C5H3){η5-1,2-[Co2(CO)6]-3,4-(Me3SiO)2-5-(Me3Si)P2C3}] Reaction of metallo-1,2-diphosphapropene (η5-tBuC5H4)(CO)2Fe? P(SiMe3)? P?C(SiMe3)2 with (Z-cyclooctene)Cr(CO)5 afforded the pentacarbonylchromium adduct of a 1,2-diphosphaferrocene [(η5-tBuC5C5H4){η5-1-[Cr(CO)5]-3,4-(Me3SiO)2-5-(Me3Si)P2C3}Fe] ( 1 c ). Diphosphaferrocene [(η5-tBuC5H4){η5-3,4-(Me3SiO)2-5-(Me3Si)P2C3}Fe] ( 2 c ) was formed when (η5-tBuC5H4)(CO)2FeBr was treated with (Me3Si)2P? P?C(SiMe3)2 in toluene at 60°C. Photolysis of molybdenum- and tungsten hexacarbonyl in the presence of [(η5-1,3-tBu2C5H3){η5-3,4-(Me3SiO)2-5-(Me3Si)P2C3}Fe] ( 2 b ) gave the pentacarbonylmetal adducts 8 (M = Mo) and 9 (M = W), respectively. A corresponding manganese derivative resulted from the photochemical reaction of 2 b and (MeC5H4)Mn(CO)3. Treatment of 2 b with Co2(CO)8 yielded trinuclear [(η5-1,3-tBu2C5H3){η5-1,2-[Co2(CO)6]-3,4-(Me3SiO)2-5-(Me3Si)P2C3}Fe] ( 11 ). Constitution and configuration of compounds 1 c, 2 c, 8 – 11 were determined by elemental analyses and spectra (IR, 1H-, 13C-, 31P-NMR, MS). In addition the molecular structure of 11 was established by single crystal X-ray analysis. 相似文献
18.
Michael P. Brwon Ahmad Yavari Ljubica Manojlovic-Muir Kenneth W. Muir Roger P. Moulding Kenneth R. Seddon 《Journal of organometallic chemistry》1982,236(1):C33-C36
[Pt(Ph2PCHPPh2)2], the first homoleptic complex containing the chelated bis(diphenylphosphino)methanide ligand, has been synthesised by reaction of K2[PtCl4] and Ph2PCH2PPh2 with KOH in ethanol, and characterised by 1H and 31P NMR spectroscopy and X-ray crystallography. 相似文献
19.
Rudolf Herrmann Armando J. L. Pombeiro 《Monatshefte für Chemie / Chemical Monthly》1986,117(4):429-435
Complextrans-[Mo(N2)2(dppe)2] (dppe=Ph
2PCH2CH2PPh
2) reacts with NN=CHCOOEt in benzene solution to afford benzene-azomethane,Ph-N=N-CH3, as the main organic product. However, the phosphazene speciesPh
2P(N2CHCOOEt)(CH2CH2)P(N2CHCOOEt)Ph
2 is formed by irradiating aTHF solution oftrans-[W(N2)2(dppe)2] in the presence of ethyldiazoacetate; in moist solution, the phosphazene bonds undergo a partial hydrolysis, and the phosphonium species [Ph
2P(NHNCHCOOEt)(CH2CH2)P(NHNCHCOOEt)Ph
2]2+ appears to be formed.
Untersuchungen zu den Reaktionen der Distickstoff-Komplexetrans-[M(N2)2(Ph 2PCH2CH2PPh 2)2] (M=Mo oder W) mit Ethyldiazoacetat: Die Bildung einer Azoverbindung und eines Phosphazens
Zusammenfassung Die Komplexetrans-[Mo(N2)2(dppe)2] (dppe=Ph 2PCH2CH2PPh 2) reagieren mit NN=CHCOOEt in benzolischer Lösung zuPh-N=N-CH3 als organischem Hauptprodukt. Andererseits wird bei der Bestrahlung vontrans-[W(N2)2(dppe)2] inTHF-Lösung in der Gegenwart von Ethyldiazoacetat das PhosphazenPh 2P(N2CHCOOEt)(CH2CH2)P(N2CHCOOEt)Ph 2 gebildet; in feuchter Lösung erleidet die Phosphazen-Bindung eine teilweise Hydrolyse und die Phosphonium-Spezies [Ph 2P(NHNCHCOOEt)(CH2CH2)P(NHNCHCOOEt)Ph 2]2+ scheint gebildet zu werden.相似文献
20.
L. Weber S. Uthmann S. Kleinebekel H.‐G. Stammler A. Stammler B. Neumann 《无机化学与普通化学杂志》2000,626(8):1831-1836
Syntheses and Structures of η1‐Phosphaallyl, η1‐Arsaallyl, and η1‐Stibaallyl Iron Complexes [(η5‐C5Me5)(CO)2Fe–E(SiMe3)C(OSiMe3)=CPh2] (E = P, As, Sb) The reaction of equimolar amounts of [(η5‐C5Me5)(CO)2Fe–E(SiMe3)2] ( 1 a : E = P; 1 b : As; 1 c : Sb) and diphenylketene afforded the η1‐phosphaallyl‐, η1‐arsaallyl‐, and η1‐stibaallyl complexes [(η5‐C5Me5)(CO)2Fe–E(SiMe3)C(OSiMe3)=CPh2] ( 2 a : E = P; 2 b : As; 2 c : Sb). The molecular structures of 2 b and 2 c were elucidated by single crystal X‐ray analyses. 相似文献