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1.
The ruthenium(II) complex Ru(CO) 2(NH 2(NH 2CH 2C 6H 5) 2(Si(C 6H 5)(CH 3) 2)I has been prepared by the reaction of Ru(CO) 4(Si(C 6H 5)(CH 3) 2)I with benzylamine. Two-dimensional homonuclear 1H NMR experiments examine the scalar coupling of the enantiotopic amino and methylene protons of the benzylamine ligand. X-ray analysis of Ru(CO) 2(NH 2CH 2C 6H 5) 2(Si(C 6H 5)(CH 3) 2)I·1/3C 5H 12 (triclinic; P
; a = 14.266(4), b = 15.748(5), c = 20.082(6) Å; = 94.38(3), β = 96.30(2), γ = 101.52(2)°) indicates three crystallographically unique complexes form a clathrate with a pentane guest. 相似文献
2.
The synthesis of the potential bridging ligand (C 6H 5) 2PCH 2CH 2Si(CH 3) 2C 5H 4 (3) is described. The ferrocene (6 derived from 3 has been found to form macrocyclic complexes with metal fragments NiCl 2, NiBr 2, and Co 2(CO) 6. Although monomeric, bimetallic products might have been expected based upon the reduced steric demands of ligand 3 relative to an analogous ligand, (C 6H 5) 2PCH 2Si(CH) 3) 2C 5H 4 (1), it appears that the increased flexibility in 3 is the overriding factor leading to a preference for inter- rather than intramolecular coordination of the second phosphine function in 6. 相似文献
3.
Reaction of YbI 2 with two equivalents of cyclopentylindenyl lithium (C 5H 9C 9H 6Li) affords ytterbium(II) substituted indenyl complex (C 5H 9C 9H 6) 2Yb(THF) 2 (1) which shows high activity to ring-opening polymerization (ROP) of lactones. The reaction between YbI 2 and cyclopentylcyclopentadienyl sodium (C 5H 9C 5H 4Na) gives complex [(C 5H 9C 5H 4) 2Yb(THF)] 2O 2 (2) in the presence of a trace amount of O 2, the molecular structure of which comprises two (C 5H 9C 5H 4) 2Yb(THF) bridged by an asymmetric O 2 unit. The O 2 unit and ytterbium atoms define a plane that contains a Ci symmetry center. 相似文献
4.
The interaction of [(η 5-C 5H 4Bu t) 2YbCl · LiCl] with one equivalent of Li[(CH 2) (CH 2)PPh 2] in tetrahydrofuran gave [Ph 2PMe 2][(η 5-C 5H 4Bu t) 2Li] (1) and [(η 5-C 5H 4Bu t) 2Yb(Cl)CH 2P(Me)Ph 2] (2) in 10% and 30% yields, respectively. 1 could also be prepared in 70% yield from the reaction of [Ph 2PMe 2][CF 3SO 3] with two equivalents of (C 5H 4Bu t)Li. Both compounds have been fully characterized by analytical, spectroscopic and X-ray diffraction methods. The solid state structure of 1 reveals a sandwich structure for the [(η 5-C 5H 4Bu t) 2Li] − anion. 相似文献
5.
A series of novel arylantimony(V) triphenylgermanylpropionates with the formula (Ph 3GeCHR 1CHR 2CO 2) nSbAr (5−n) (R 1=H, Ph; R 2=H, CH 3; n=1, 2) were synthesized and characterized by elemental analysis, IR, 1H-NMR, 13C-NMR and mass spectroscopy. The crystal structures of Ph 3GeCH(Ph)CH 2CO 2SbPh 4 and [Ph 3GeCH 2CH(CH 3)CO 2] 2Sb(4-ClC 6H 4) 3 were determined by X-ray diffraction. The in vitro antitumor activities of some selected compounds against five cancer cells are reported. 相似文献
6.
The reactions of RNHSi(Me) 2Cl (1, R= t-Bu; 2, R=2,6-(Me 2CH) 2C 6H 3) with the carborane ligands, nido-1-Na(C 4H 8O)-2,3-(SiMe 3) 2-2,3-C 2B 4H 5 (3) and Li[ closo-1-R′-1,2-C 2B 10H 10] (4), produced two kinds of neutral ligand precursors, nido-5-[Si(Me) 2N(H)R]-2,3-(SiMe 3) 2-2,3-C 2B 4H 5, (5, R= t-Bu) and closo-1-R′-2-[Si(Me) 2N(H)R]-1,2-C 2B 10H 10 (6, R= t-Bu, R′=Ph; 7, R=2,6-(Me 2CH) 2C 6H 3, R′=H), in 85, 92, and 95% yields, respectively. Treatment of closo-2-[Si(Me) 2NH(2,6-(Me 2CH) 2C 6H 3)]-1,2-C 2B 10H 11 (7) with three equivalents of freshly cut sodium metal in the presence of naphthalene produced the corresponding cage-opened sodium salt of the “carbons apart” carborane trianion, [ nido-3-{Si(Me) 2N(2,6-(Me 2CH) 2C 6H 3)}-1,3-C 2B 10H 11] 3− (8) in almost quantitative yield. The reaction of the trianion, 8, with anhydrous MCl 4 (M=Ti and Zr) in 1:1 molar ratio in dry tetrahydrofuran (THF) at −78 °C, resulted in the formation of the corresponding half-sandwich neutral d 0-metallacarborane, closo-1-M[(Cl)(THF) n]-2-[1′-η 1σ-N(2,6-(Me 2CH) 2C 6H 3)(Me) 2Si]-2,4-η 6-C 2B 10H 11 (M=Ti (9), n=0; M=Zr (10), n=1) in 47 and 36% yields, respectively. All compounds were characterized by elemental analysis, 1H-, 11B-, and 13C-NMR spectra and IR spectra. The carborane ligand, 7, was also characterized by single crystal X-ray diffraction. Compound 7 crystallizes in the monoclinic space group P2 1/ c with a=8.2357(19) Å, b=28.686(7) Å, c=9.921(2) Å; β=93.482(4)°; V=2339.5(9) Å 3, and Z=4. The final refinements of 7 converged at R=0.0736; wR=0.1494; GOF=1.372 for observed reflections. 相似文献
7.
Reaction of ansa-cyclopentadienyl pyrrolyl ligand (C 5H 5)CH 2(2-C 4H 3NH) (2) with Ti(NMe 2) 4 affords bis(dimethylamido)titanium complex [(η 5-C 5H 4)CH 2(2-C 4H 3N)]Ti(NMe 2) 2 (3) via amine elimination. A cyclopentadiene ligand with two pendant pyrrolyl arms, a mixture of 1,3- and 1,4-{CH 2(2-C 4H 3NH)} 2C 5H 4 (4), undergoes an analogous reaction with Ti(NMe 2) 4 to give [1,3-{CH 2(2-C 4H 3N)} 2(η 5-C 5H 3)]Ti(NMe 2) (5). Molecular structures of 3 and 5 have been determined by single crystal X-ray diffraction studies. 相似文献
8.
LnCl 3 (Ln=Nd, Gd) reacts with C 5H 9C 5H 4Na (or K 2C 8H 8) in THF (C 5H 9C 5H 4 = cyclopentylcyclopentadienyl) in the ratio of 1 : to give (C 5H 9C 5H 4)LnCl 2(THF) n (orC 8H 8)LnCl 2(THF) n], which further reacts with K 2C 8H 8 (or C 5H 9C 5H 4Na) in THF to form the litle complexes. If Ln=Nd the complex (C 8H 8)Nd(C 5H 9C 5H 4)(THF) 2 (a) was obtained: when Ln=Gd the 1 : 1 complex [(C 8H 8)Gd(C %H 9)(THF)][(C 8H 8)Gd(C 5H 9H 4)(THF) 2] (b) was obtained in crystalline form. The crystal structure analysis shows that in (C8H8)Ln(C5H9C5H4)(THF)2 (Ln=Nd or Gd), the Cyclopentylcyclopentadieny (η5), cyclooctatetraenyl (η8) and two oxygen atoms from THF are coordinated to Nd3+ (or Gd3+) with coordination number 10. The centroid of the cyclopentadienyl ring (Cp′) in C5H9C5H4 group, cyclooctatetraenyl centroid (COTL) and two oxygens (THF) form a twisted tetrahedron around Nd3+ (or Gd3+). In (C8H8)Gd(C5H9C5H4)(THF), the cyclopentyl-cyclopentadienyl (η5), cyclooctatetraenyl (η8) and one oxygen atom are coordinated to Gd3+ with the coordination number of 9 and Cp′, COT and oxygen atom form a triangular plane around Gd3+, which is almost in the plane (dev. -0.0144 Å). 相似文献
9.
Mononuclear halfsandwich transition metal complexes (Cp*M) are useful model compounds in which one hemisphere of the coordination shell is blocked by the voluminous Cp* ring. In the protected space below the Cp* ligand, one or two 1,2-dicarba-closo-dodecarborane-1,2-dichalcogenolate ligands can be accommodated, e.q. a mono-dichalcogenolate carborane halfsandwich iridium complexes Cp*Ir(E 2C 2B 10H 10)(E=S, Se)[l] and bis-dichalcogenolate carborane rhenium or tungsten complexes Cp*Re(E 2C 2B 10H 10) 2(E=S, Se,Te),[Li(THF) 4] [Cp*W(E 2C 2B 10H 10) 2] (E=S, Se). 相似文献
10.
The complex (di-η 5-C 5H 4CH 2CH 2CH 2C 5H 4)Ti(η 1-C 5H 5) 2 (I) can be obtained unambiguously starting from the corresponding bridged titanocene dichloride. Attempts to synthesize the isomeric compounds (η 5-C 5H 5) 2 Ti(di-η 1-C 5H 4-CH 2CH 2CH 2C 5H 4) (I′) by the action of a convenient bridged dianion on (C 5H 5) 2 TiCl 2 afford several compounds, one of them is the complex I. The possibility of interconversion of these complexes by a fluctional process is discussed. 相似文献
11.
Treatment of 1,2- trans-C 5H 8(PCl 2) 2 with 1,2-C 2H 4(NHPr- i) 2 gave the C2-symmetric perhydro-1,6,2,5-diazaphosphocine C 5H 8{P(Cl)N(Pr- i)CH 2} 2- cyclo, which produced dissymmetric C 5H 8(PPh 2){P[N(Pr- i)CH 2] 2- cyclo} on further reaction with PhMgBr. Cleavage of the P---N bonds with gaseous HCl afforded C 5H 8(PPh 2)(PCl 2), which was converted to C 5H 8(PPh 2){P(OPh) 2} 2 by reaction with phenol. All chiral P, P derivatives were obtained as racemates as well as resolved (1 R,2 R)- and (1 S,2 S)-enantiomers. 相似文献
12.
The reaction between RMgCl (two equivalents) and 1,2-W 2Cl 2(NMe 2) 4 in hydrocarbon solvents affords the compounds W 2R 2(NMe 2) 4, where R = allyl and 1− and 2-methyl-allyl. In the solid state the molecular structure of W 2(C 3H 5) 2(NMe 2) 4 has C2 symmetry with bridging allyl ligands and terminal W---NMe 2 ligands. The W---W distance 2.480(1) Å and the C---C distances, 1.47(1) Å, imply an extensive mixing of the allyl π-MOs with the WW π-MOs, and this is supported by an MO calculation on the molecule W 2(C 3H 5) 2(NH 2) 4 employing the method of Fenske and Hall. The most notable interaction is the ability of the (WW) 6+ centre to donate to the allyl π *-MO (π 3). This interaction is largely responsible for the long W---W distance, as well as the long C---C distances, in the allyl ligand. The structure of the 2-methyl-allyl derivative W 2(C 4H 7) 2(NMe 2) 4 in the solid state reveals a gauche-W 2C 2N 4 core with W---W = 2.286(1) Å and W---C = 2.18(1) Å, typical of WW and W---C triple and single bonds, respectively. In solution (toluene-d 8) 1H and 13C NMR spectra over a temperature range −80°C to +60°C indicate that both anti- and gauche- W 2C 2N 4 rotamers are present for the 2-methyl-allyl derivative. In addition, there is a facile fluxional process that equilibrates both ends of the 2-methyl-allyl ligand on the NMR time-scale. This process leads to a coalescence at 100°C and is believed to take place via an η 3-bound intermediate. The 1-methyl-allyl derivative also binds in an η 1 fashion in solution and temperature-dependent rotations about the W---N, W---C and C=C bonds are frozen out at low temperatures. The spectra of the allyl compound W 2(C 3H 5) 2(NMe 2) 4 revealed the presence of two isomers in solution—one of which can be readily reconciled with the presence of the bridging isomer found in the solid state while the other is proposed to be W 2(η 3-C 3H 5) 2(NMe 2) 4. The compound W 2R 2(NMe 2) 4 where R = 2,4-dimethyl- pentadiene was similarly prepared and displayed dynamic NMR behaviour explainable in terms of facile η 1 = η 3 interconversions. 相似文献
13.
Thermal displacement of coordinated nitriles RCN (R = CH 3, C 2H 5 or n-C 3H 7) in [C 5H 5Fe(L 2)(NCR)]X complexes (L 2 = P(OCH 3) 3) 2, (P(OC 6H 5) 3) 2 or (C 6H 5) 2PC 2H 4P(C 6H 5) 2 (DPPE)) by E(CH 3) 2 affords high yields of [C 5H 5Fe(L 2)(E(CH 3) 2)]X compounds (E = S, Se and Te; X = BF 4 or PF 6). Spectroscopic data and ligand displacement reactions are presented and discussed together with related observations on [C 5H 5Fe(CO) 2(E(CH 3) 2)]BF 4 compounds. The molecular structure of [C 5H 5Fe(P(OCH 3) 3) 2(S(CH 3) 2)]PF 6 was determined by a single-crystal X-ray diffraction study: monoclinic, space group P2 1/ n- C52h (No. 14) with a = 8.4064(12), b = 11.183(2), c = 50.726(8) Å, β = 90.672(13)° and Z = 8 molecules per unit cell. The coordination sphere of the iron atom is pseudo-tetrahedral with an Fe---S bond distance of 2.238 Å. 相似文献
14.
The compounds (π-C 5H 5)(CO) 2LM-X (L = CO, PR 3; M = Mo, W; X = BF 4, PF 6, AsF 6, SbF 6) react with H 2S, p-MeC 6H 4SH, Ph 2S and Ph 2SO(L′) to give ionic complexes [(π-C 5H 5)(CO) 2LML′] + X −. Also sulfur-bridged complexes, [(π-C 5H 5)(CO) 3W---SH---W(CO) 3(π-C 5H 5)] + AsF 6− and [(π-C 5H 5)(CO) 3M-μ-S 2C=NCH 2Ph-M(CO) 3(π-C 5H 5)], have been obtained. Reactions with SO 2 and CS 2 have been examined. 相似文献
15.
Anhydrous monoaryllead triacetates ArPb(OAc) 3 (Ar = Ph, p-Tolyl, o-Tolyl, 2,5-Xylyl; OAc = OCOMe) were prepared by arylation of Pb(OAc) 4 with ArSn(C 4H 9- n) 3 in the presence of Hg(OCOCF 3) 2. The procedure was adapted for the synthesis of diaryllead diacetates Ar 2Pb(OAc) 2 (Ar = Ph, p-Tolyl, o-Tolyl, p-ClC 6H 4, o-ClC 6H 4) and afforded products with higher purity than other procedures. The crystal structures of PhPb(OAc) 3, Ph 2Pb(OAc) 2 and ( o-Tolyl) 2Pb(OAc) 2 were determined by X-ray diffraction. PhPb(OAc) 3 and ( o-Tolyl) 2Pb(OAc) 2 are monomeric. The pentagonal bipyramid around Pb in PhPb(OAc) 3, like the trapezoidal bipyramid around Pb in ( o-Tolyl) 2Pb(OAc) 2, is heavily distorted, the OAc groups being unsymmetrically chelating. Lead in Ph 2Pb(OAc) 2 is in a distorted octahedral environment. One OAc group is bridging, linking the molecular units to infinite chains, the other OAc group is symmetrically chelating. IR, 1H, 13C and 207Pb NMR spectroscopic data are reported. The structures of p-TolPb(OAc) 3, o-TolPb(OAc) 3 and 2,5-XylPb(OAc) 3 are inferred to be similar to that of PhPb(OAc) 3, and the structure of ( o-ClC 6H 4) 2Pb(OAc) 2 is inferred to be similar to that of ( o-Tolyl) 2Pb(OAc) 2. 相似文献
16.
Novel isonitrile derivatives of a diruthenium carbonyl complex, (μ 2,η 3:η 5-guaiazulene)Ru 2(CO) 5 (2), were synthesized by substitution of a CO ligand by an isonitrile, and were subjected to studies on thermal and photochemical haptotropic interconversion. Treatment of 2 (a 45:55 mixture of two haptotropic isomers, 2-A and 2-B) with RNC at room temperature resulted in coordination of RNC and alternation of the coordination mode of the guaiazulene ligand to form (μ 2,η 1:η 5-guaiazulene)Ru 2(CO) 5(CNR), 5d–5f, [5d; R= tBu, 5e; 2,4,6-Me 3C 6H 2, or 5f; 2,6- iPr 2C 6H 3] in moderate to good yields. Thermal dissociation of a CO ligand from 5 at 60 °C resulted in quantitative formation of a desirable isonitrile analogue of 2, (μ 2,η 3:η 5-guaiazulene)Ru 2(CO) 4(CNR), 4d–4f, [4d; R= tBu, 4e; 2,4,6-Me 3C 6H 2, or 4f; 2,6- iPr 2C 6H 3], as a 1:1 mixture of the two haptotropic isomers. A direct synthetic route from 2 to 4d–4f was alternatively discovered; treatment of 2 with one equivalent of RNC at 60 °C gave 4d–4f in moderate yields. All of the new compounds were characterized by spectroscopy, and structures of 5d (R= tBu) and 4d-A (R= tBu) were determined by crystallography. Thermal and photochemical interconversion between the two haptotropic isomers of 4d–4f revealed that the isomer ratios in the thermal equilibrium and in the photostatic state were in the range of 48:52–54:46. 相似文献
17.
The optically active indenyl complexes ((η 5-C 9H 7)Ru(L---L)Cl (where L---L is either ( S, S)-1,2-dimethyl-1,2-ethanediylbis(diphenylphosphine) (chiraphos) or ( R, R)-1,2-cyclopentanediylbis(diphenylphosphine) (cypenphos)) have been synthesized and spectroscopically characterized and compared with the corresponding cyclopentadienyl complexes. Reaction of the new complexes with 2-e-donors give cationic adducts in which the pentahaptocoordination of the indenyl ligand is maintained. The crystal structures of ( S, S)-(η 5-C 9H 7)Ru{Ph 2PCH(CH 3)CH(CH 3)PPh 2}Cl (1) and ( S, S)-η 5-C 5H 5Ru{Ph 2PCH(CH 3)CH(CH 3)PPh 2}Cl (3) have been determined. 相似文献
18.
The diphenylbutadiene-bridged gadolinium complex [GdCl 2(THF) 3] 2( μ-Ph 2C 4H 4) · 3THF (1) has been obtained by the reaction of Gd(III) chloride with diphenylbutadienepotassium. The molecular structure of 1 was determined by X-ray diffraction. The complex 1 has a binuclear structure in which a bridging diphenylbutadiene ligand is η4-bonded to the Gd atoms connecting two GdCl 2(THF) 3 units. Both Gd atoms have a distorted octahedral environment. At the Gd atom the two Cl atoms are in trans positions and the four other coordination sites are occupied by the three O atoms of THF molecules and the η4-bonded C 4H 4 fragment of a diphenylbutadiene ligand. In the two η4-bonded GdC 4H 4 fragments one of the Gd-C η4-distances is significantly elongated (2.86(3) and 2.97(3) Å) compared with other three (2.65(3)–2.69(3) and 2.67(3)—2.77(3) Å). The magnetic moment of Gd, equal to 8.1 BM, is typical for Gd 3+ compounds that is evidence for a formal charge of DPBD ligand of −2 in complex 1. However, the expected distribution of the C-C bond of the diene fragment as long—short—long is not realized. 相似文献
19.
The reaction of Ru(CO) 4(C 2H 4) or Ru(CO) 5 with 1,5-Ph 4P 2N 4S 2 in CH 2Cl 2/hexane at 23°C produces the dimer [Ru(CO) 2(Ph 4 P 2N 4S 2)] 2 (2), which was shown by X-ray crystallography to have a centrosymmetric structure in which the P 2N 4S 2 ring is attached to one ruthenium atom through two (geminal) nitrogen atoms and the remote sulfur atom and serves as a bridge to the other ruthenium atom via the second sulfur atom. Crystals of 2 ·2(CH 2Cl 2) are triclinic, space group P
(No. 2), a = 12.901(1) Å, b = 13.072(1) Å, c = 10.123(1) Å, = 100.88(1)°, β = 98.90(1)°, γ = 67.50(1)°, V = 1542.4(3) Å, Z = 1 with final R and Rw values of 0.040 and 0.027, respectively. 相似文献
20.
The P-functional organotin dichloride [Ph 2P(CH 2) 3] 2SnCl 2 (3) is synthesized by reaction of Ph 2P(CH 2) 3MgCl with SnCl 4 independently of the molar ratio of the starting compounds. The corresponding organotin trichlorides Ph 2P(CH 2) nSnCl 2R (4: n=2, R=Cl; 5: n=3, R=Cl; 6: n=3, R=Me) are formed in a cleavage reaction of Ph 2P(CH 2) nSnCy 3 ( n=2, 3) with SnCl 4 or MeSnCl 3, respectively. The main features of the crystal structures of 3–6 are both intra- and intermolecular PSn coordinations and the existence of intermolecular Sn---ClSn bridges. For further characterization of the title compounds, the adducts 4(Ph 3PO) 2 (7) and 5(Ph 3PO) (8), as well as the P-oxides and P-sulfides of 3–6 (9–15), are synthesized. The results of crystal structure analyses of 7, 11, 12, and 14 are reported. The structures of 9–15 are characterized by intramolecular P=XSn interactions (X=O, S). A first insight into the structural behavior of the compounds 3–15 in solution is discussed on the basis of multinuclear NMR data. 相似文献
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