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1.
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
2.
A series of isomalononitrile dithiolato palladium complexes, (PPh 3) 2Pd(1-mnt) (1), [P(OPh) 3] 2Pd( i-mnt) (2), (PPh 3)(py)Pd( i-mnt)·CH 3CN (4), (Et 4N) 2Pd( i-mnt) 2 (4) and (Ph 4As) 2Pd( i-mnt) 2 (5) were synthesized and characterized by elemental analysis and IR spectroscopy. The reaction between (Et 4N) 2Pd( i-mnt) 2 (4) and (Et 4N) 2WS 4 gave a mixed metal cluster (Et 4N) 2WS 4Pd( i-mnt) (6). The crystallographically determined structures of 1 and 6 are reported. 相似文献
3.
The geometric structures and conformational properties of trifluoromethanesulfonic anhydride, (CF 3SO 2) 2O, and bis(trifluoromethylsulfonyl)difluoromethane, (CF 3SO 2) 2CF 2 have been studied by gas electron diffraction (GED) and ab initio calculations (HF/3–21G*). The calculations predict for both systems two stable conformers with C2 symmetry and one with C1 symmetry. In both compounds structures with C2 symmetry and dihedral angles SOSC ≈ 100° ((CF 3SO 2) 2O) and SCSC≈ 150° ((CF 3SO 2) 2CF 2 are lowest in energy. According to the GED analyses the dominant conformer of (CF 3SO 2) 2O 2 possesses C2 symmetry with SOSC dihedral angles of 99.1(14)°. The presence of up to 30% of the two other conformers cannot be excluded; for (CF 3SO 2) 2CF 2 only one conformer with C2 symmetry and SCSC dihedral angles of 143(2)° is observed. A complete set of geometric parameters is given. 相似文献
4.
The geometric structures and conformational properties of trifluoromethanesulfonic anhydride, (CF 3SO 2) 2O, and bis(trifluoromethylsulfonyl)difluoromethane, (CF 3SO 2) 2CF 2 have been studied by gas electron diffraction (GED) and ab initio calculations (HF/3–21G*). The calculations predict for both systems two stable conformers with C2 symmetry and one with C1 symmetry. In both compounds structures with C2 symmetry and dihedral angles SOSC ≈ 100° ((CF 3SO 2) 2O) and SCSC ≈ 150° ((CF 3SO 2) 2CF 2) are lowest in energy. According to the GED analyses the dominant conformer of (CF 3SO 2) 2O possesses C2 symmetry with SOSC dihedral angles of 99.1(14)°. The presence of up to 30% of the two other conformers cannot be excluded; for (CF 3SO 2) 2CF 2 only one conformer with C2 symmetry and SCSC dihedral angles of 143(2)° is observed. A complete set of geometric parameters is given. 相似文献
5.
Synthesis, structure, spectroscopy and thermal properties of complex [Co(NCS) 2(hmt) 2(H 2O) 2][Co(NCS) 2(H 2O) 4] (H 2O) (I), assembled by hexamethylenetetramine and octahedral Co(II) metal ions, are reported. Crystal data for I: Fw 387.34, a=9.020(8), b=12.887(9), c=7.95(1) Å, =96.73(4), β=115.36(5), γ=94.16(4)°, V=820(1) Å 3, Z=2, space group= P−1, T=173 K, λ(Mo-K )=0.71070 Å, ρcalc=1.718567 g cm −3, μ=17.44 cm −1, R=0.088, Rw=0.148. An interesting two-dimensional network is assembled via hydrogen bonds through coordinated and free water molecules. The d–d transition energy levels of Co(II) ion are determined by UV–vis spectroscopy and calculated by ligand field theory. The calculated results agree well with experiment ones. 相似文献
6.
Infrared and Raman spectra on Na 3H(SO 4) 2, K 3 H(SO 4) 2 and (NH 4) 3 H(SO 4) 2 crystals have been investigated at 300 and 100 K in the 4000 to 30 cm −1 region. An assignment of bands in terms of OH group frequencies and more or less distorted tetrahedra of ammonium and sulphate ions is given. The crystallographic and spectroscopic symmetry and/or dissymetry of OHO hydrogen bonds linking sulphate ions into dimers is discussed using OH group frequencies and the splitting of the v1 (SO 4) Raman bands as criteria. In the particular case of (NH 4) 3H(SO 4) 1 compound containing several solid phases it can be shown that the room temperature phase (II) is strongly disordered, principally because of an orientational disorder of ammonium ions, and that a progressive ordering takes place with temperature lowering. 相似文献
7.
The compounds K 4Ti(O 2) 4·2H 2O, K 3Ta(O 2) 2F 4 and K 2V 2O 3(O 2) 2F 2 undergo photolysis in the solid state. The photolysis kinetics obey the parabolic rate equation p = kt1/2 and indicate a monoexcitation process for the photolysis. These features are similar to those reported previously for peroxo complexes. The mechanism of evolution of oxygen reported earlier appears to be the same in all these solids. 相似文献
8.
The molecular structure of [Zr(NMe 2) 4] 2 has been determined by an x-ray study and shown to involve a central Zr 2N 8 moiety involving the fusing of two trigonal bipyramidal units along a common axial-equatorial edge. The terminal Zr---NMe 2 units have trigonal planar coordination about the nitrogen atoms: Zr---N = 2.050(5) and 2.104(5) Å, and Zr---N (bridge) = 2.224(3) and 2.453(4) Å for equatorial and axial bonds, respectively. The Zr---Zr distance is 3.704(1) Å as expected for a non-M---M bonding bridged compound. In tetrahydrofuran solution, Zr(NMe 2) 4 and LiNMe 2 react irreversibly giving Zr(NMe 2) 6 Li 2(THF) 2 which has been isolated and characterized by an X-ray study. The central ZrN 6 octahedral moiety is capped on two opposite faces by Li atoms which are also coordinated to an oxygen atom of a THF molecule. Pertinent distances are: Zr---N = 2.22(7) (av.), N---Li = 2.155(25) (av.) and Li---O = 1.915(10) Å. 相似文献
9.
Estertn compounds, (MeO 2CCH 2CH 2) 2SnX 2 [X 2 = I 2 (2); X 2 = Br 2 (9); X 2 = Cl, Br (4)) or X 2 = (NCS) 2 (3)] have been obtained by halide exchange reactions of (MeO 2CCH 2CH 2) 2SnCl 2. Crystal structure determinations of 2–4 revealed chelating MeO 2CCH 2CH 2 units with distorted octahedral geometries at tin. The Sn---O bond lengths in the isothiocyanato complex, 3, are shorter [2.390(11) to 2.498(12), mean 2.439 Å], with the chelate bite angles, C---Sn---O, larger [74.3(7) to 78.2(6), mean 76.0°] than those in the halide analogues 2 and 4 [Sn---O = 2.519(2) to 2.541(8), mean 2.530 Å; C---Sn---O 72.8(3) to 73.9(4), mean 73.3°]. 1H, 13C and 119Sn NMR and IR spectra of 2–4 and 9 were determined in CDCl 3 solution: the NMR spectra of (MeO 2CCH 2CH 2) 2SnX 2 show the following trends: (i) both δ 1H and δ 13C , increase and (ii) both 2J (Sn---H) and 1J( Sn--- C) decrease in the sequence X 2 = (NCS) 2, Cl 2, ClBr, Br 2 and I 2. The MeO 2CCH 2CH 2 and dmio groups (dmio = 1,3-dithiole-2-one-4,5-dithiolato) are all chelating groups in (MeO 2CCH 2CH 2) 2Sn(dmio) (5). As shown by X-ray crystallography, the tin atom in the anion of solid [Q][MeO 2CCH 2CH 2Sn(dmio) 2] 6 (Q = NEt 4) forms 5 strong bonds [to C and the 4 thiolato S atoms, Sn---S 2.459(2) to 2.559(2) Å], arranged in a near trigonal bipyramidal array. There is an additional Intramolecular but weaker, interaction with the carbonyl oxygen atom [Sn---O = 3.111(5) Å]; v(C=O) = 1714 cm −1 in solid 6 (Q = NEt 4). NMR spectra of 5 and 6 are also reported. 相似文献
10.
Addition of 1,4-dithiols to dichloromethane solutions of [PtCl 2(P-P)] (P-P = (PPh 3) 2, Ph 2P(CH 2) 3PPh 2, Phd 2P(CH 2) 4PPh 2; 1,4-dithiols = HS(CH 2) 4SH, (−)DIOSH 2 (2,3- O-isopropylidene-1,4-dithiol-l-threitol), BINASH 2 (1,1′-dinaphthalene-2,2′-dithiol)) in the presence of NEt 3 yielded the mononuclear complexes [Pt(1,4-dithiolato)(P-P)]. Related palladium(II) complexes [Pd(dithiolato)(P-P)] (P-P=Ph 2P(CH 2) 3PPh 2, Ph 2P(CH 2) 4PPh 2; dithiolato = −S(CH 2) 4S −, (−)-DIOS) were prepared by the same method. The structure of [Pt((−)DIOS)(PPh 3) 2] and [Pd(S(CH 2) 4S)(Ph 2P(CH 2) 3PPh 2)] complexes was determined by X-ray diffraction methods. Pt—dithiolato—SnC1 2 systems are active in the hydroformylation of styrene. At 100 atm and 125°C [Pt(dithiolate)(P-P)]/SnCl 2 (Pt:Sn = 20) systems provided aldehyde conversion up to 80%. 相似文献
11.
The coordinating properties of the trifluoromethyl elemental compounds Me 2PP(CF 3) 2 and Me 2AsP(CF 3) 2 have been studied by the synthesis and spectroscopic investigations (IR, NMR, MS) of their complexes cis-M(CO) 4L 2 (A), [(CO) 4ML] 2 (B) and [(CO) 5M] 2L (C) (M = Cr, Mo, W). Complexes of type A with L = Me 2PP(CF 3) 2 are obtained in good yield by reaction with M(CO) 4NBD (NBD = norbornadiene), whereas with L = Me 2AsP(CF 3) 2 the homobinuclear compounds B are formed. The attempt to prepare the cis-M(CO) 4[Me 2AsP(CF 3) 2] 2 complexes by treating M(CO) 4(Me 2AsH) 2 with P 2(CF 3) 4 is successful only for M = W. Binuclear compounds of type B or C, in general, can be prepared by stepwise reaction of the ligands with either M(CO) 4NBD or M(CO) 5THF. 相似文献
12.
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
13.
(C 6H 5) 3MX 2 (M = As, Sb; X = OCOCF 3 and M = Sb, Bi; X = SO 3F, SO 3CF 3) compounds prepared by the interaction of triphenylmetal(V) substrates with (CF 3CO) 2O, (CF 3SO 2) 2O and (FSO 2) 2O have been characterized by molecular weight determination, elemental and spectroscopic (IR, 1H and 19F NMR, mass) analyses. 相似文献
14.
The observed difference in transition strength for (SF 6) 2, (SiF 4) 2 and (SiH 4) 2 IR-predissociation spectra is explained by induction effects (μ 012/ R126) which have to be included in the interaction Hamiltonian in addition to the dominant dipole-dipole term (μ 012/ R123). 相似文献
15.
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
16.
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
17.
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
18.
Two fluoride sulfates,K 2Mn 3(SO 4) 3F 2·4H 2O(Ⅰ) and Rb 2Mn 3(SO 4) 3F 2·2H 2O (Ⅱ) are obtained by water solution method.Single-crystal X-ray diffraction analysis indicated that they crystallize in space groups of Cmc2 1.Their structures feature a pseudo-KTP structure consisting of interconnecting[Mn 3(SO 4)3F 2(H 2O)2] ∞ layers,which are further packing along the a axis with alkali metal cations balancing the charges.The structure relationships between the two compounds are discussed.Secondharmonic generation measurements manifest that Ⅰ and Ⅱ have similar second-harmonic generation responses of about 0.2 and 0.25 times that of KH 2PO 4. 相似文献
19.
Dissolution of Mo 2O 5((CH 3) 2NCH 2CH 2NHCH 2CH 2S) 2 in dimethylformamide results in the formation of a species without coordinated sulphur, as indicated by 95Mo NMR spectroscopy. Subsequent crystallization of this solution yielded the compound Mo 4O 12(C 12H 30N 4S 2) 2(C 3H 7ON) 2 which X-ray crystallography shows to consist of a novel Mo 4O 12 core, containing an eight-membered Mo 4O 4 ring with the two pairs of diagonal molybdenum atoms linked by disulphido-containing groups. 相似文献
20.
The binuclear molybdenum(II) complexes [Mo 2(O 2CCF 3) 4(PR 3) 2] (R = Ph, Et) act as templates for the self-condensation of 2-aminobenzaldehyde to give a new class of complexes in which a hydride ion bridges two molybdenum(III) centres, each of which carries a tetradentate macrocyclic ligand (C). The new hydrido complexes [Mo 2(C) 2 (H)(O 2CCF 3) 3(PPh 3) 2] (I), [Mo 2(C) 2(H) 2(O 2CCF 3) 2(PPh 3) 2] (II), and [Mo 2(C) 2 (H) 2(O 2CCF 3) 2(PEt 3) 2] 2 (V) exist in two or more isomeric forms as shown by their IR, 1H, 31P and 19F NMR spectra. Substitution with thiocyanate, nitrate and tetraphenylborate anions gives the new products [Mo 2(C) 2(H)(CO)(NCS) 3(PPh 3) 2] (III), [Mo 2(C) 2 (H) 2(O 2CCF 3)(NO 3)(PPh 3) 2] (IV), [Mo 2(C) 2(H)(O 2CCF 3)(PPh 3) 2](BPh 4) 2 (VI) and [Mo 2(C) 2(H) 2(O 2CCF 3)(PEt 3) 2](BPh 4) (VII), which also exist in isomeric forms. 相似文献
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