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1.
The Dihydridoiridium(III) Complex [IrH2Cl(P i Pr3)2] as a Molecular Building Block for Unsymmetrical Binuclear Rhodium–Iridium and Iridium–Iridium Compounds The title compound [IrH2Cl(PiPr3)2] ( 3 ) reacts with the chloro‐bridged dimers [RhCl(PiPr3)2]2 ( 1 ) and [IrCl(C8H14)(PiPr3)]2 ( 5 ) by cleavage of the Cl‐bridges to give the unsymmetrical binuclear complexes 4 and 6 with Rh(μ‐Cl)2Ir and Ir(μ‐Cl)2Ir as the central building block. The reactions of 3 with the bis(cyclooctene) and (1,5‐cyclooctadiene) compounds [MCl(C8H14)2]2 ( 7 , 8 ) and [MCl(η4‐C8H12)]2 ( 9 , 10 ) (M = Rh, Ir) occur analogously and afford the rhodium(I)‐iridium(III) and iridium(I)‐iridium(III) complexes 11 – 14 in 70–80% yield. Treatment of [(η4‐C8H12)M(μ‐Cl)2IrH2(PiPr3)2] ( 13 , 14 ) with phenylacetylene leads to the formation of the substitution products [(η4‐C8H12)M(μ‐Cl)2IrH(C≡CPh)(PiPr3)2] ( 15 , 16 ) without changing the central molecular core. Similarly, the compound [(η4‐C8H12)Rh(μ‐Br)2IrH(C≡CPh)(PiPr3)2] ( 18 ) has been prepared; it was characterized by X‐ray crystallography. 相似文献
2.
Syntheses, Structure and Reactivity of η3‐1,2‐Diphosphaallyl Complexes and [{(η5‐C5H5)(CO)2W–Co(CO)3}{μ‐AsCH(SiMe3)2}(μ‐CO)] Reaction of ClP=C(SiMe2iPr)2 ( 3 ) with Na[Mo(CO)3(η5‐C5H5)] afforded the phosphavinylidene complex [(η5‐C5H5)(CO)2Mo=P=C(SiMe2iPr)2] ( 4 ) which in situ was converted into the η1‐1,2‐diphosphaallyl complex [η5‐(C5H5)(CO)2Mo{η3‐tBuPPC(SiMe2iPr)2] ( 6 ) by treatment with the phosphaalkene tBuP=C(NMe2)2. The chloroarsanyl complexes [(η5‐C5H5)(CO)3M–As(Cl)CH(SiMe3)2] [where M = Mo ( 9 ); M = W ( 10 )] resulted from the reaction of Na[M(CO)3(η5‐C5H5)] (M = Mo, W) with Cl2AsCH(SiMe3)2. The tungsten derivative 10 and Na[Co(CO)4] underwent reaction to give the dinuclear μ‐arsinidene complex [(η5‐C5H5)(CO)2W–Co(CO)3{μ‐AsCH(SiMe3)2}(μ‐CO)] ( 11 ). Treatment of [(η5‐C5H5)(CO)2Mo{η3‐tBuPPC(SiMe3)2}] ( 1 ) with an equimolar amount of ethereal HBF4 gave rise to a 85/15 mixture of the saline complexes [(η5‐C5H5)(CO)2Mo{η2‐tBu(H)P–P(F)CH(SiMe3)2}]BF4 ( 18 ) and [Cp(CO)2Mo{F2PCH(SiMe3)2}(tBuPH2)]BF4 ( 19 ) by HF‐addition to the PC bond of the η3‐diphosphaallyl ligand and subsequent protonation ( 18 ) and/or scission of the PP bond by the acid ( 19 ). Consistently 19 was the sole product when 1 was allowed to react with an excess of ethereal HBF4. The products 6 , 9 , 10 , 11 , 18 and 19 were characterized by means of spectroscopy (IR, 1H‐, 13C{1H}‐, 31P{1H}‐NMR, MS). Moreover, the molecular structures of 6 , 11 and 18 were determined by X‐ray diffraction analysis. 相似文献
3.
Synthesis and Crystal Structure of the Complexes [(n‐Bu)4N]2[{(THF)Cl4Re≡N}2PdCl2], [Ph4P]2[(THF)Cl4Re≡N‐PdCl(μ‐Cl)]2 and [(n‐Bu)4N]2[Pd3Cl8] The threenuclear complex [(n‐Bu)4N]2[{(THF)Cl4Re≡N}2 PdCl2] ( 1 ) is obtained in THF by the reaction of PdCl2(NCC6H5)2 with [(n‐Bu)4N][ReNCl4] in the molar ration 1:2. It forms orange crystals with the composition 1· THF crystallizing in the monoclinic space group C2/c with a = 2973.3(2); b = 1486.63(7); c = 1662.67(8)pm; β = 120.036(5)° and Z = 4. If the reaction is carried out with PdCl2 instead of PdCl2(NCC6H5)2, orange crystals of hitherto unknown [(n‐Bu)4N]2[Pd3Cl8] ( 3 ) are obtained besides some crystals of 1· THF. 3 crystallizes with the space group P1¯ and a = 1141.50(8), b = 1401.2(1), c = 1665.9(1)pm, α = 67.529(8)°, β = 81.960(9)°, γ = 66.813(8)° and Z = 2. In the centrosymmetric complex anion [{(THF)Cl4Re≡N}2PdCl2]2— a linear PdCl2 moiety is connected in trans arrangement with two complex fragments [(THF)Cl4Re≡N]— via asymmetric nitrido bridges Re≡N‐Pd. For Pd(II) thereby results a square‐planar coordination PdCl2N2. The linear nitrido bridges are characterized by distances Re‐N = 163.8(7)pm and Pd‐N = 194.1(7)pm. The crystal structure of 3 contains two symmetry independent, planar complexes [Pd3Cl8]2— with the symmetry 1¯, in which the Pd atoms are connected by slightly asymmetric chloro bridges. By the reaction of equimolar amounts of [Ph4P][ReNCl4] and PdCl2(NCC6H5)2 in THF brown crystals of the heterometallic complex, [Ph4P]2[(THF)Cl4Re≡N‐PdCl(μ‐Cl)]2 ( 2 ) result. 2 crystallizes in the monoclinic space group P21/n with a = 979.55(9); b = 2221.5(1); c = 1523.1(2)pm; β = 100.33(1)° and Z = 2. In the central unit ClPd(μ‐Cl)2PdCl of the centrosymmetric anionic complex [(THF)Cl4Re≡N‐PdCl(μ‐Cl)]22— the coordination of the Pd atoms is completed by two nitrido bridges Re≡N‐Pd to nitrido complex fragments [(THF)Cl4Re≡N]— forming a square‐planar arrangement for Pd(II). The distances in the linear nitrido bridges are Re‐N = 163.8(9)pm and Pd‐N = 191.5(9)pm. 相似文献
4.
Oliver Buttler Amal Al‐Fawaz Deborah L. Kays Joanna K. Day Li‐Ling Ooi Simon Aldridge 《无机化学与普通化学杂志》2006,632(14):2187-2189
Halide abstraction from [(Ph3P)2Rh(μ‐Cl)]2 by the sodium salt of the weakly coordinating [BArf4]? anion [Arf = C6H3(CF3)2‐3,5] in the presence of excess arene offers a convenient, high‐yielding route to the half‐sandwich cations [(arene)Rh(PPh3)2]+[BArf4]? [arene = benzene ( 1 ), toluene ( 2 )]. Crystalline samples of 1 and 2 are isomorphous [a = 13.1270(2), b = 15.3030(2), c = 17.5760(3) Å, α = 74.620(1), β = 81.533(1), γ = 88.540(1)° for 1 ] and feature the arene ligand bound to the rhodium atom in η6 fashion. 相似文献
5.
Hans‐Christian Bttcher Marion Graf Kurt Merzweiler Christoph Wagner 《无机化学与普通化学杂志》2001,627(5):903-908
Heterobinuclear Complexes: Synthesis and X‐ray Crystal Structures of [RuRh(μ‐CO)(CO)4(μ‐PtBu2)(tBu2PH)], [RuRh(μ‐CO)(CO)3(μ‐PtBu2)(μ‐Ph2PCH2PPh2)], and [CoRh(CO)4(μ‐H)(μ‐PtBu2)(tBu2PH)] [Ru3Rh(CO)7(μ3‐H)(μ‐PtBu2)2(tBu2PH)(μ‐Cl)2] ( 2 ) yields by cluster degradation under CO pressure as main product the heterobinuclear complex [RuRh(μ‐CO)(CO)4(μ‐PtBu2)(tBu2PH)] ( 4 ). The compound crystallizes in the orthorhombic space group Pcab with a = 15.6802(15), b = 28.953(3), c = 11.8419(19) Å and V = 5376.2(11) Å3. The reaction of 4 with dppm (Ph2PCH2PPh2) in THF at room temperature affords in good yields [RuRh(μ‐CO)(CO)3(μ‐PtBu2)(μ‐dppm)] ( 7 ). 7 crystallizes in the triclinic space group P 1 with a = 9.7503(19), b = 13.399(3), c = 15.823(3) Å and V = 1854.6 Å3. Moreover single crystals of [CoRh(CO)4(μ‐H)(μ‐PtBu2)(tBu2PH)] ( 9 ) could be obtained and the single‐crystal X‐ray structure analysis revealed that 9 crystallizes in the monoclinic space group P21/a with a = 11.611(2), b = 13.333(2), c = 18.186(3) Å and V = 2693.0(8) Å3. 相似文献
6.
Synthesis and Crystal Structure of the Nitrido Complexes [(n‐Bu)4N]2[{(L)Cl4Re≡N}2PtCl2] (L = THF und H2O) and [(n‐Bu)4N]2[(H2O)Cl4Re≡N‐PtCl(μ‐Cl)]2 The threenuclear complex [(n‐Bu)4N]2[{(THF)Cl4Re≡N}2—PtCl2] ( 1a ) is obtained by the reaction of [(n‐Bu)4N][ReNCl4] with [PtCl2(C6H5CN)2] in THF/CH2Cl2. It forms red crystals with the composition 1a · 2 CH2Cl2 crystallizing in the tetragonal space group I41/a with a = 3186.7(2); c = 1311.2(1) pm and Z = 8. If the reaction of the educts is carried out without THF, however under exposure to air the compound [(n‐Bu)4N]2[{(H2O)Cl4Re≡N}2PtCl2] ( 1b ) is obtained as red trigonal crystals with the space group R3 and a = 3628.3(3), c = 1231.4(1) pm and Z = 9. In the centrosymmetric complex anions [{(L)Cl4Re≡N}2PtCl2]2— a linear PtCl2moiety is connected in a trans arrangement with two complex fragments [(L)Cl4Re≡N]— via asymmetric nitrido bridges Re≡dqN‐Pt. For PtII such results a square‐planar coordination PtCl2N2. The linear nitrido bridges are characterized by distances Re‐N = 169.5 pm and Pt‐N = 188.8 pm ( 1a ), respectively, Re‐N = 165.6 pm and Pt‐N = 194.1 pm ( 1b ). By the reaction of [(n‐Bu)4N][ReNCl4] with PtCl4 in CH2Cl2 platinum is reduced forming the heterometallic ReVI/PtII complex, [(n‐Bu)4N]2[(H2O)Cl4Re≡N‐PtCl(μ‐Cl)]2 ( 2 ). It crystallizes in the monoclinic space group C2/c with a = 2012.9(1); b = 1109.0(2); c = 2687.4(4) pm; β = 111.65(1)° and Z = 4. In the central unit ClPt(μ‐Cl)2PtCl of the anionic complex [(H2O)Cl4Re≡N‐PtCl(μ‐Cl)]22— with the symmetry C2 the coordination of the Pt atoms is completed by two nitrido bridges Re≡N‐Pt to nitrido complex fragments [(H2O)Cl4Re≡N] — forming a square‐planar arrangement for the Pt atoms. The distances in the linear nitrido bridges are Re‐N = 165.9 pm and Pt‐N = 190.1 pm. 相似文献
7.
The synthesis and single crystal X‐ray structure determination are reported for the 2,2′ : 6′,2″‐terpyridine (= tpy) adduct of bismuth(III) nitrate. The hydroxide‐bridged dimer [(η2‐NO3)2(tpy)Bi(μ‐OH)2Bi(tpy)(η2‐NO3)2] with nine‐coordinate geometry about Bi was the only isolable product from all crystallization attempts in varying ratios of Bi(NO3) : terpy.; [(η2‐NO3)2(tpy)Bi(μ‐OH)2Bi(tpy) · (η2‐NO3)2] is triclinic, P 1, a = 7.941(8), b = 10.732(9), c = 11.235(9) Å; α = 63.05(1), β = 85.01(1), γ = 79.26(1)°, Z = 1, dimer, R = 0.058 for N0 = 2319. 相似文献
8.
Deprotonation of the readily available organometallic aldehyde derivative [(η4‐C7H7CHO)Fe(CO)3] ( 2 ) with NaN(SiMe3)2 in benzene solution at ambient temperature afforded the anionic formylcycloheptatrienyl complex Na[(η3‐C7H6CHO)Fe(CO)3] ( 3 ). The anion is fluxional in solution and displays a unique ambident reactivity towards electrophiles (MeI, Me3SiCl). New substituted [(η4‐RC7H6CHO)Fe(CO)3] and [(η4‐heptafulvene)Fe(CO)3] complexes have been identified as the products. Treatment of 3 with 0.5 equivalents of dimeric [(COD)RhCl]2 (COD = 1,5‐cyclooctadiene) afforded the functionalized Fe‐Rh cycloheptatrienyl complex [(μ‐C7H6CHO)(CO)3FeRh(COD)] ( 7 ) in up to 86 % yield. Carbonylation of 7 under an atmosphere of CO led to facile conversion to the heterobimetallic pentacarbonyl derivative [(μ‐C7H6CHO)(CO)3FeRh(CO)2] ( 8 ), which is also accessible in lower yield from the direct reaction of 3 with [Rh(CO)2Cl]2. 相似文献
9.
Feng‐Bo Xu Li‐Juan Sun Zhen‐Ai Xuan Wei‐Dong Zhang Hui Cheng Zheng‐Zhi Zhang 《中国化学》2000,18(5):722-728
Reaction of a new type of bidentate ligand PhPQu [PhPQu = 2‐diphenylphosphino‐4‐methylquinoline] with Fe(CO)5 in butanol gave trans‐Fe(FpPQu‐P)(CO)3 (1). Compound 1, which can act as a neutral tridentate organometallic ligand, was reacted with I B, II B metal compounds and a rhodium complex to give six binuclear complexes with Fe? M bonds, Fe(CO)3 (μ‐Ph2PQu)MXn (2–7) [M= Zn(II), Cd(II), Hg(II), Cu(I), Ag(I), Rh(I)], and an ion‐pair complex [Fe(CO)3 (μ‐Ph2PQu)2HgI][HgI3]? (8). The structure of 8 was determined by X‐ray crystallography. Complex 8 crystallizes in the space group P‐1 with a = 1.0758(3), b = 1.6210(4), c=1.7155(4)nm; a=75.60(2), β=71.81(2), γ=81.78(2)° and Z = 2 and its structure was refined to give agreement factors of R=0.050 and Rw = 0.057. The Fe‐Hg bond distance is 0.2536nm. 相似文献
10.
Ingo Krossing Ulli Englert Eberhard Matern Jolanta Olkowska‐Oetzel Jerzy Pikies Gerhard Fritz 《无机化学与普通化学杂志》2002,628(2):446-452
tBu2P‐P=P(Me)tBu2 reacts with [Fe2(CO)9] to give [μ‐(1, 2, 3:4‐η‐tBu2P1‐P2‐P3‐P4tBu2){Fe(CO)3}{Fe(CO)4}] ( 1 ) and [trans‐(tBu2MeP)2Fe(CO)3]( 2 ). With [(η2‐C8H14)2Fe(CO)3] in addition to [μ‐(1, 2, 3:4‐η‐tBu2P1‐P2‐P3‐P4tBu2){Fe(CO)2PMetBu2}‐{Fe(CO)4}] ( 10 ) and 2 also [(μ‐PtBu2){μ‐P‐Fe(CO)3‐PMetBu2}‐{Fe(CO)3}2(Fe‐Fe)]( 9 ) is formed. 1 crystallizes in the monoclinic space group P21/c with a = 875.0(2), b = 1073.2(2), c = 3162.6(6) pm and β = 94.64(3)?. 2 crystallizes in the monoclinic space group P21/c with a = 1643.4(7), b = 1240.29(6), c = 2667.0(5) pm and β = 97.42(2)?. 9 crystallizes in the monoclinic space group P21/n with a = 1407.5(5), b = 1649.7(5), c = 1557.9(16) pm and β = 112.87(2)?. 相似文献
11.
Helmut Goesmann Eberhard Matern Jolanta Olkowska‐Oetzel Jerzy Pikies Gerhard Fritz 《无机化学与普通化学杂志》2001,627(6):1181-1184
Coordination Chemistry of P‐rich Phosphanes and Silylphosphanes. XXIII. Reactions of tBu2P–P=P(Me)tBu2 with (Et3P)2NiCl2 and [{η2‐C2H4}Ni(PEt3)2] tBu2P–P=P(Me)tBu2 ( 1 ) forms with (Et3P)2NiCl2 ( 2 ) and Na(Nph) the [μ‐(1,3 : 2,3‐η‐tBu2P4tBu2){Ni(PEt3)Cl}2] ( 3 ) as main product. Using Na/Hg instead as reducing agent the Ni0 compounds [{η2‐tBu2P–P}Ni(PEt3)2] ( 4 ), [{η2‐tBu2P–P=P–PtBu2}Ni(PEt3)2] ( 5 ) and [(Et3P)Ni(μ‐PtBu2)]2 ( 6 ) with four‐membered Ni2P2 ring result. [{η2‐C2H4}Ni(PEt3)2] yields with 1 also 4 . The compounds were characterized by 1H and 31P{1H} NMR investigations and 3 also by a single crystal X‐ray analysis. It crystallizes triclinic in the space group P 1 with a = 1129.4(2), b = 1256.8(3), c = 1569.5(3) pm, α = 72.44(3)°, β = 70.52(3)° and γ = 74.20(3)°. 相似文献
12.
The Conjugative Bridging of Organometallic Reaction Centers in Heterodinuclear Complexes [(OC)3ClRe(μ‐L)MCl(C5Me5)]+, M = Rh or Ir ‐ Spectroscopic Consequences of Reductive Activation Heterodinuclear complexes [(OC)3ClRe(μ‐L)MCl(C5Me5)](PF6), M = Rh or Ir and L = 2, 5‐bis(1‐phenyliminoethyl)pyrazine (bpip), 3, 6‐bis(2‐pyridyl)‐1, 2, 4, 5‐tetrazine (bptz) or 2, 2′‐bipyrimidine (bpym), were synthesized via mononuclear rhenium compounds (L)Re(CO)3Cl. The stepwise reductive activation under chloride dissociation was studied through cyclic voltammetry and spectroelectrochemistry in the range of CO stretching vibrations (IR), charge transfer absorptions (UV/Vis) and electron spin resonance (ESR) for paramagnetic intermediates of the mono‐ and heterodinuclear compounds. While complexes of bpip and bptz form one‐electron reduced radical intermediates [(OC)3ClRe(μ‐L)MCl(C5Me5)] ˙ , the compounds with bpym react under MCl‐dissociative two‐electron reduction directly to [(OC)3ClRe(μ‐L)M(C5Me5)]. 相似文献
13.
The reactions of Cp*M(PMe3)Cl2 (M = Rh ( 1a ), Ir ( 1b )) with (NEt4)2[WS4] led to the heterodimetallic sulfido‐bridged complexes Cp*M(PMe3)[(μ‐S)2WS2] (M = Rh ( 2a ), Ir ( 2b )), whereas the dimers [Cp*MCl(μ‐Cl)]2 (M = Rh ( 4a ), Ir ( 4b )) reacted with (NEt4)2[WS4) to give the known trinuclear compounds [Cp*M(Cl)]2(μ‐WS4) (M = Rh ( 5a ), Ir ( 5b )). Hydrolysis of the terminal W=S bonds converts 2a, b into Cp*M(PMe3)[(μ‐S)2WO2] (M = Rh ( 3a ), Ir ( 3b )). Salts of a heterodimetallic anion, A[CpMo(I)(NO)(WS4)] ( 6 ) (A+ = NEt4+, NPh4+) were obtained by reactions of [CpMo(NO)I2]2 with tetrathiotungstates, A2[WS4]. The complexes were characterized by IR and NMR (1H, 13C, 31P) spectroscopy, and the X‐ray crystallographic structure of Cp*Rh(PMe3)[(μ‐S)2WS2] ( 2a ) has been determined. The bond lengths and angles in the coordinations spheres of Rh and W in 2a (Rh···W 288.5(1) pm) are compared with related complexes containing terminal [WS42—] chelate ligands. 相似文献
14.
Reaction of [Ru(η6‐p‐cymene)Cl2]2 with two equivalents of [Ph4P][Cl] in CH2Cl2 yields [Ph4P][Ru(η6‐p‐cymene)Cl3], containing a trichlororuthenate(II) anion. In solution, an equilibrium between the product and [Ru(η6‐p‐cymene)Cl2]2 is observed, which in CDCl3 is nearly completely shifted to the dimer, whereas in CD2Cl2 essentially a 1:1‐mixture of the two ruthenium species is present. Crystallization from CH2Cl2/pentane yielded two different crystals, which were identified by X‐ray analysis as [Ph4P][Ru(η6‐p‐cymene)Cl3] and [Ph4P][Ru(η6‐p‐cymene)Cl3]·CH2Cl2. 相似文献
15.
Synthesis and Dynamic Behaviour of [Rh2(μ-H)3H2(PiPr3)4]+. Contributions to the Reactivity of the Tetrahydridodirhodium Complex [Rh2H4(PiPr3)4] An improved synthesis of [Rh2H4(PiPr3)4] ( 2 ) from [Rh(η3-C3H5)(PiPr3)2] ( 1 ) or [Rh(η3-CH2C6H5)(PiPr3)2] ( 3 ) and H2 is described. Compound 2 reacts with CO or CH3OH to give trans-[RhH(CO)(PiPr3)2] ( 4 ) and with ethene/acetone to yield a mixture of 4 and trans-[RhCH3(CO)(PiPr3)2] ( 5 ). The carbonyl(methyl) complex 5 has also been prepared from trans-[RhCl(CO)(PiPr3)2] ( 6 ) and CH3MgI. Whereas the reaction of 2 with two parts of CF3CO2H leads to [RhH2(η2-O2CCF3) · (PiPr3)2] ( 8 ), treatment of 2 with one equivalent of CF3CO2H in presence of NH4PF6 gives the dinuclear compound [Rh2H5(PiPr3)4]PF6 ( 9a ). The reactions of 2 with HBF4 and [NO]BF4 afford the complexes [Rh2H5(PiPr3)4]BF4 ( 9b ) and trans-[RhF(NO)(PiPr3)2]BF4 ( 11 ), respectively. In solution, the cation [Rh2(μ-H)3H2(PiPr3)4]+ of the compounds 9a and 9b undergoes an intramolecular rearrangement in which the bridging hydrido and the phosphane ligands are involved. 相似文献
16.
A novel mixed‐tribridged dimolybdenum(I) compound [Bn4N][Mo2(μ‐SPh)2(μ‐Cl)(CO)6] (1) has been synthesized from the reaction of Mo2(CO)3(SPh)2 with BU4NCl. Compound 1 was characterized by IR, UV‐Vis and 1H, 13C, 95Mo NMR spectroscopic analyses. The electrochemical behavior was measured by cyclic voltammetry, indicating a quasi‐reversible two‐electron transfer in one step. The crystal structure determined by X‐ray crystallography shows that 1 contains a [Mo2(μ‐S)2(μ‐Cl)]? core with a planar Mo2S2unit and a Cl bridge. The Mo? Mo distance is 0.28709(7) nm, and the Mo‐Cl‐Mo angle is 66.44(4)°. A newface‐sharing bioctahedral structure is discussed. 相似文献
17.
Six novel organometallic half sandwich complexes [(η5‐C5Me5)M(L1–3)Cl]Cl.2H2O were synthesized using [{(η5‐C5Me5)M(μ‐Cl)Cl2], where M = Ir (III)/Rh (III) and L1–3 = three pyridyl pyrimidine based ligands; and characterized by NMR, Infra‐red spectroscopy, conductance, elemental and thermal analysis. The complex‐DNA binding mode and/or strength evaluated using absorption titration, electrochemical studies and hydrodynamic measurement proposed intercalative binding mode, which was also confirmed by molecular docking study. Differential pulse voltammetry and cyclic voltammetry studies indicated an alteration in oxidation and reduction potentials of complexes (M+4/M+3) in presence of CT‐DNA. The metal complexes can cleave plasmid DNA as proposed in gel electrophoretic analysis. The LC50 values of complexes evaluated on brine shrimp suggested their potent cytotoxic nature. 相似文献
18.
Synthesis and Spectroscopic Characterization of [Rh(SeCN)6]3– and trans ‐[Rh(CN)2(SeCN)4]3–, Crystal Structure of (Me4N)3[Rh(SeCN)6] Treatment of RhCl3 with KSeCN in acetone yields a mixture of selenocyanato‐rhodates(III), from which [Rh(SeCN)6]3– and trans‐[Rh(CN)2(SeCN)4]3– have been isolated by ion exchange chromatography on diethylaminoethyl cellulose. The X‐ray structure determination on a single crystal of (Me4N)3[Rh(SeCN)6] (trigonal, space group R3, a = 14.997(2), c = 24.437(3) Å, Z = 6) reveals, that the compound crystallizes isotypically to (Me4N)3[Ir(SCN)6]. The exclusively via Se coordinated selenocyanato ligands are bonded with the average Rh–Se distance of 2.490 Å and the Rh–Se–C angle of 104.6°. In the low temperature IR and Raman spectra the metal ligand stretching modes ν(RhSe) of (n‐Bu4N)3[Rh(SeCN)6] ( 1 ) and trans‐(n‐Bu4N)3[Rh(CN)2(SeCN)4] ( 2 ) are in the range of 170–250 cm–1. In 2 νas(CRhC) is observed at 479 cm–1. The vibrational spectra are assigned by normal coordinate analysis based on the molecular parameters of the X‐ray determination. The valence force constants are fd(RhSe) = 1.08 ( 1 ), 1.10 ( 2 ) and fd(RhC) = 3.14 mdyn/Å ( 2 ). fd(RhS) = 1.32 mdyn/Å is determined for [Rh(SCN)6]3–, which has not been calculated so far. The 103Rh NMR resonances are 2287 ( 1 ), 1680 ppm ( 2 ) and the 77Se NMR resonances are –32.7 ( 1 ) and –110.7 ppm ( 2 ). The Rh–C bonding of the cyano ligand in 2 is confirmed by a dublett in the 13C NMR spectrum at 136.3 ppm. 相似文献
19.
Cluster Complexes [M2Rh(μ‐PCy2)(μ‐CO)2(CO)8] with Triangular Core of RhM2 (M = Re, Mn; M2 = MnRe): Synthesis, Structure, Ring Opening Reaction, and Properties as Catalysts for Hydroformylation and Isomerisation of 1‐Hexene The salts PPh4[M2(μ‐H)(μ‐PCy2)(CO)8] and Rh(COD)[ClO4] were in equimolar amounts reacted at –40 to –15 °C in the presence of CO(g) in CH2Cl2/methanol solution under release of PPh4[ClO4] to intermediates. Such species formed in a selective reaction the unifold unsaturated 46 valence electrons title compounds [M2Rh(μ‐PCy2)(μ‐CO)2(CO)8] (M = Re 1 , Mn 2 ; M2 = MnRe 3 ) in yields of > 90%; analogeous the derivatives with the PPh2 bridge could the obtained (M = Re 4 , Mn 5 ). From these clusters the molecular structure of 2 was determined by a single crystal X‐ray analysis. The exchange of the labil CO ligand attached at the rhodium ring atom in 1 – 3 against selected tertiary and secondary phosphanes in solution gave the substitution products [M2RhL(μ‐PCy2)(μ‐CO)2(CO)7] (M = Re: L = PMe3 6 , P(n‐Bu)3 7 , P(n‐C6H4SO3Na)3 8 , HPCy2 9 , HPPh2 10 , HPMen2 11 , M2 = MnRe: L = HPCy2 12 ) nearly quantitative. Such dimanganese rhodium intermediates ligated with secondary phosphanes were converted in a subsequent reaction to the ring‐opened complexes [MnRh(μ‐PCy2)(μ‐H)(CO)5Mn(μ‐PR2)(CO)4] (M = Mn: R = Cy 13 , Ph 14 , Mn 15 ). The molecular structure of 13 , which showed in the time scale of the 31P NMR method a fluxional behaviour, was determined by X‐ray structure analysis. All products obtained were always characterized by means of υ(CO)Ir, 1H and 31P NMR measurements. From the reactants of hydroformylation process, CO(g) 1 – 2 in different solvents afforded at 20 °C under a reversible ring opening reaction the valence‐saturated complexes [MRh(μ‐PCy2)(CO)7M(CO)5] (M = Re 16 , Mn 17 ), whereas the reaction of CO(g) and the ring‐opened 13 to [MnRh(μ‐PCy2)(μ‐H)(CO)6Mn(μ‐PCy2)(CO)4] ( 18 ) was as well reversible. The molecular structures of 17 and 18 were determined by X‐ray analysis. The υ(CO)IR, 1H and 31P NMR measurements in pressure‐resistant reaction vessels at 20 °C ascertained the heterolytic splitting of hydrogen in the reaction of 1 – 2 dissolved in CDCl3 or THF‐d8 under formation of product monoanions [M2Rh(μ‐CO)(μ‐H)(μ‐PCy2)(CO)9]– (M = Re, Mn), which also were formed by the reaction of NaBH4 and 1 – 2 . Finally, the substrate 1‐hexene and 1 and 3 gave under the release of the labil CO ligand an η2‐coordination pattern of hexene, which was weekened going from the Re to the Mn neighbor atoms. After the results of the catalytic experiments with 1 and 2 as catalysts, such change in the bonding property revealed an advantageous formation of hydroformylation products for the dirhenium rhodium catalyst 1 and that of isomerisation products of hexene for the dimanganese rhodium catalyst 2 . Par example, 1 generated n‐heptanal/2‐methylhexanal in TOF values of 246 [h–1] (n/iso = 3.4) and the c,t‐hexenes in that of 241 [h–1]. Opposotite to this, 2 achieved such values of 55 [h–1] (n/iso = 3.6) and 473 [h–1]. A triphenylphosphane substitution product of 1 increased the activity of the hydroformylation reaction about 20%, accompanied by an only gradually improved selectivity. The hydrogenation products like alcohols and saturated hydrocarbons known from industrial hydroformylation processes were not observed. The metals manganese and rhenium bound at the rhodium reaction center showed a cooperative effect. 相似文献
20.
Darstellung und Kristallstruktur eines Ditelluridovanadium(IV)‐Komplexes: [(μ‐η1‐Te2)(μ‐NtBu)2V2Cp2]
Synthesis and Crystal Structure of a Ditelluridovanadium(IV) Complex: [(μ‐η1‐Te2)(μ‐NtBu)2V2Cp2] [(μ‐η1‐Te2)(μ‐NtBu)2V2Cp2] ( 2 ) is formed from [tBuN = VCp(PMe3)2] ( 1 ) upon reaction with elemental tellurium. 1 and 2 are characterized by spectroscopic methods (MS; 1H, 13C, 51V NMR), in addition 2 by single crystal X‐ray diffraction. The crystal structure indicates a folded cyclodivanadazen ring bridged by a bidentated ditellurido ligand, the first example of this structure type. 相似文献