共查询到20条相似文献,搜索用时 46 毫秒
1.
Alkylidene complexes (Me 3SiCH 2) 3Ta(PMe 3)=CHSiMe 3 (1) and Me 3SiCH 2Ta(PMe 3) 2(=CHSiMe 3) 2 (3a) were found to react with phenylsilanes H 2SiR′Ph (R′=Me, Ph) and (PhSiH 2) 2CH 2 to give disilyl-substituted alkylidenes (Me 3SiCH 2) 3Ta=C(SiMe 3)(SiHR′Ph) (2) and novel metallasilacyclobutadiene and metalladisilacyclohexadiene complexes. Silyl-substituted alkylidene complex (Bu tCH 2) 2W(=O)[=C(Bu t)(SiPh 2Bu t)] (5a) was prepared from the reaction of O 2 with an equilibrium mixture (Bu tCH 2)W(=CHBu t) 2(SiPh 2Bu t) (4b) (Bu tCH 2) 2W(CBu t)(SiPh 2Bu t) (4a). Our recent studies of the preparation of these complexes and mechanistic pathways in the formation of these silyl-substituted alkylidene complexes are summarized. 相似文献
2.
The syntheses of the 1,3,5-trimethyl- and tri- tert-butyl-1,3,5-triazacyclohexane-supported imido complexes [M(NR)(R′ 3tach)Cl 2] (M = Ti or Zr (NMR only); R = Bu t or 2,6-C 6H 3Pr i2; R′ = Me or Bu t) are reported, along with that of the thermally robust dibenzyl derivative [Ti(NBu t)(Me 3tach)(CH 2Ph) 2]. The tert-butylimido ligand in [Ti(NBu t)(Me 3tach)Cl 2] undergoes exchange with ArNH 2 (Ar = 4-C 6H 4Me or 2,6-C 6H 4Me or 2,6-C 6H 3Pr i2) to form the corresponding arylimides [Ti(NAr)(Me 3tach)Cl 2]. The Me 3tach ring in [Ti(NR)(Me 3tach)Cl 2] undergoes slow exchange with Bu t3tach or Me 3tacn (1,4,7-trimethyl-1,4,7-triazacyclononane) to give the ring-exchanged products [Ti(NR)(Bu t3tach)Cl 2] and [Ti(NR)(Me 3tacn)Cl 2], respectively. The complexes [Ti(NR)(Me 3tach)X 2] (R = Bu t or 2,6-C 6H 3Pr i2; X = Cl or CH 2Ph) exhibit room-temperature dynamic NMR behaviour via an unusual trigonal twist of the facially coordinated Me 3tach ligand, and the activation parameters for these processes have been measured and are discussed. The X-ray structures of [Ti(NR)(Bu t3tach)Cl 2] (R = Bu t or 2,6-C 6H 3Pr i2) and [Ti(NBu t)(Me 3tach)(X) 2] [X= Cl or CH 2Ph) are reported. Me 3tach and Bu t3tach = 1,3,5-trimethyl- and tri- tert-butyl-1,3,5-triazacyclohexane, respectively. 相似文献
3.
Recent results (post-1990) on the synthesis and structures of bis(trimethylsilyl)methyls M(CHR 2) m (R = SiMe 3) of metals and metalloids M are described, including those of the crystalline lipophilic [Na(μ-CHR 2)] ∞, [Rb(μ-CHR 2)(PMDETA)] 2, K 4(CHR 2) 4(PMDETA) 2, [Mg(CHR 2)(μ-CHR 2)] ∞, P(CHR 2) 2 (gaseous) and P 2(CHR 2) 4, [Yb(CHR 2) 2(OEt 2) 2] and [{Yb(CR 3)(μ-OEt)(OEt 2)} 2]; earlier information on other M(CHR 2) m complexes and some of their adducts is tabulated. Treatment of M(CHR 2) (M = Li or K) with four different nitriles gave the X-ray-characterized azaallyls or β-diketinimates
,
and
(LL′ = N(R)C( tBu)CHR, L′L′ = N(R)C(Ph)C(H)C(Ph)NR, LL″ = N(R)C(Ph)NC(H)C(Ph)CHR, R = SiMe 3 and Ar = C 6H 3Me 2-2,5). The two lithium reagents were convenient sources of other metal azaallyls or β-diketinimates, including those of K, Co(II), Zr(IV), Sn(IV), Yb(II), Hf(IV) and U(VI)/U(III). Complexes having one or more of the bulky ligands [LL′] −, [L′L′] −, [LL] −, [LL″] −, [L″L] −, [LL] − and [{N(R)C( tBu)CH} 2C 6H 4-2] 2− are described and characterized (LL = N(H)C(Ph)C(H)C(Ph)NH, L″L = N(R)C( tBu)C(H)C(Ph)NR, LL = N(R)C( tBu)CHPh). Among the features of interest are (i) the contrasting tetrahedral or square-planar geometry for
and
, respectively, and (ii) olefin-polymerization catalytic activity of some of the zirconium(IV) chlorides. 相似文献
4.
To examine the steric effects on the stability of Ln(0) π-arene compounds, molecular mechanics (MMP2) calculations are performed on Gd(η-C 6H 6) 2 and Ln(η-Bu t3C 6H 3) 2 (where Ln is Gd, Yb and Y ). The small potential-well depth ( ≈ 2 kcal mol −1) and the large Gd-C equilibrium distance ( > 3.3 Å) explains the instability of Gd(η-C 6H 6) 2, while the difference in the stability between Gd(η-Bu t3C 6H 3) 2 and Yb(η-Bu t3C 6H 3) 2 can be attributed to the difference in the van der Waalsradii of the two metals and the more contracted 5d orbitals on the Yb atom. 相似文献
5.
Treatment of p-tert-butylcalix[6]areneH 6 (H 6L) with [Mo(OBu t) 2{[2,2′-( N)-C 6H 4] 2(CH 2CH 2)}] in refluxing toluene affords, after work-up, the complex [Mo(2-NC 6H 4CH 2CH 2C 6H 4NHC(Me)NH-2 /)LH 2]·4MeCN (1), which contains an 11-membered metallocyclic ring as characterised by Synchrotron X-radiation. 相似文献
6.
The reactions of BrMn(CO) 5 with the non-chelating stereochemically rigid bidentate ligands (L-L) 1,3-, and 1,4-diisocyanobenzene, 4,4′-diisocyanobiphenyl, and 4,4′-diisocyanodiphenylmethane afford well characterized complexes of the types BrMn(CO) 4(L-L), BrMn(CO) 3(L-L) 2, and [BrMn(CO) 4] 2(L-L). Similar reactions with [RC 5H 4Mn(CO) 2NO] +PF 6− gave mixtures of oligomers of the type [(RC 5H 4MnNO) n(L-L) n+1] n+[PF 6−] n. 相似文献
7.
The synthesis of the homoleptic molybdenum imido compound Li 2Mo(NBu t) 4 is reported. The complexes M (NBu t) 2(NHBu t) 2 (M = Mo, W) can be protonated with various strong acids giving neutral species. The X-ray crystal structure of the tungsten complex W (NBu t) 2(NH 2Bu t) 2 (SO 3CF 3) 2 confirms the presence of O-coordinated cis- CF 3SO 3 groups. 相似文献
8.
The aryldiazenido ligands provide the fourth member of the isoelectronic series CO, NO +, RNC, RN 2+ of ligands for transition metal complexes. The first aryldiazenido metal complex was reported in 1964 when p-CH 3OC 6H 4N 2Mo(CO) 2C 5H 5 was prepared by the reaction of NaMo(CO) 3C 5H 5 with p-CH 3OC 6H 4N 2+BF 4−. This review surveys the development of organometallic aryldiazenido chemistry since that time. Such organometallic aryldiazenido derivatives, including RN 2M(CO) 2C 5H 5, RN 2M(CO) 2(Pz 3BH) (M = Cr, Mo, W), [(η 6-Me 6C 6)Cr(CO) 2N 2Ar] +, [(MeC 15H 4)M′(CO) 2N 2Ar] + M′ = Mn, Re), [ trans-PhN 2Fe(CO) 2(PPh 3) 2] +, and PhN 2M′(CO) 2(PPh 3) 2(PPh 3) 2 can be obtained by reactions of arenediazonium salts with suitably chosen transition metal nucleophiles. Analogous methods cannot be used to prepare alkyldiazenido transition metal complexes because of the instability of alkyldiazonium salts. However, the alkyldiazenido derivatives RCH 2N 2M(CO) 2C 5H 5 (R = H or Me 3Si) can be obtained from HM(CO) 3C 5H 5 and the corresponding diazoalkanes. Important aspects of the chemical reactivity of RN 2M(CO) 2Q derivatives (Q = C 5H 5, Pz 3BH) include CO substitution reactions, coordination of the second nitrogen in the RN 2 ligand to give heterobimetallic complexes such as C 5H 5Mo(CO) 2(μ-NNC 6H 4Me)(CO) 2C 5H 5, oxidative addition rections with X 2 X = Cl, Br, I), SnX 4, RSSR, and CINO, and reactions with further RN 2+ to give bis(aryldiazenido) derivatives (RN 2) 2MQL + (L = CO, X −, etc.). Dearylation of an aryldiazenido ligand to a dinitrogen ligand can be effected by reaction of [(MeC 5H 4)M′(CO) 2N 2Ar] + with certain nucleophiles to give (MeC 5H 4)M′(CO) 2N 2. 相似文献
9.
The neutral nitrogen-bidentate ligand, diphenylbis(3,5-dimethylpyrazol-1-yl)methane, Ph 2CPz′ 2, can readily be obtained by the reaction of Ph 2CCl 2 with excess HPz′ in a mixed-solvent system of toluene and triethylamine. It reacts with [Mo(CO) 6] in 1,2-dimethoxyethane to give the η 2-arene complex, [Mo(Ph 2CPz′ 2)(CO) 3] (1). This η 2-ligation appears to stabilize the coordination of Ph 2CPz′ 2 in forming [Mo(Ph 2CPz′ 2)(CO) 2(N 2C 6H 4NO 2- p)][BPh 4] (2) and [Mo(Ph 2CPz′ 2)(CO) 2(N 2Ph)] [BF 4] (3) from the reaction of 1 with the appropriate diazonium salt but the stabilization seems not strong enough when [Mo{P(OMe) 3} 3(CO) 3] is formed from the reaction of 1 with P(OMe) 3. The solid-state structures of 1 and 3 have been determined by X-ray crystallography: 1-CH 2Cl 2, monoclinic, P2 1/ n, a = 11.814(3), b = 11.7929(12), c = 19.46 0(6) Å, β = 95.605(24)°, V = 2698.2(11) Å 3, Z = 4, Dcalc = 1.530 g/cm 3 , R = 0.044, Rw = 0.036 based on 3218 reflections with I > 2σ( I); 2 (3)-1/2 hexane-1/2 CH 3OH-1/2 H 2O-1 CH 2Cl 2, monoclinic, C2/ c, a = 41.766(10), b = 20.518(4), c = 16.784(3) Å, β = 101.871(18)°, V = 14076(5) Å 3, Z = 8, Dcalc = 1.457 g/cm 3, R = 0.064, Rw = 0.059 based on 5865 reflections with I > 2σ( I). Two independent cations were found in the asymmetric unit of the crystals of 3. The average distance between the Mo and the two η 2-ligated carbon atoms is 2.574 Å in 1 and 2.581 and 2.608 Å in 3. The unfavourable disposition of the η 2-phenyl group with respect to the metal centre in 3 and the rigidity of the η 2-arene ligation excludes the possibility of any appreciable agostic C---H → Mo interaction. 相似文献
10.
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
11.
The reactions of MnRe(CO) 10 with As 2(CF 3) 4 and MnCo(CO) 9 with P 2(CF 3) 4, As 2(CF 3) 4, S 2(CF 3) 2, Se 2(CF 3) 2, (CF 3) 2EI (E = P, As), (CF 3) 2AsH, (CF 3) 2AsE′CF 3 (E′ = S, Se), (CF 3) 2PSeCF 3, Me 2AsI and (CF 3) 2PPMe 2, respectively, have been studied under various conditions. Besides already known mono- and binuclear compounds the heteronuclear complexes MnRe(CO) 8[As(CF 3) 2] 2 and MnCo(CO) 7[E(CF 3) 2] 2 (E = P, As) are formed. The reactions proceed via cleavage of the M---M′ bond and formation of the mononuclear species Mn(CO) 5X and M′(CO) nY (M′ = Re, n = 5; M′ = Co, n = 4). 相似文献
12.
The sterically hindered zinc chalcogenolato complexes [Zn(EAr″) 2] 2 (E = S, Se; Ar″ = 2,4,6-Bu t3C 6H 2) react with 1 equivalent of tert-butylisocyanide in non-coordinating solvents to give Zn(EC 6H 2Bu t3) 2(CNBu t) (1, E = S; 2, E = Se) as thermally stable crystalline adducts; the compounds are thought to be chalcogenolato-bridged dimers. In the presence of excess isocyanide ligand the 1 : 2 adducts Zn(EAr″) 2(CNBu t) 2 (3, E = S; 4, E = Se) are isolated. The compounds represent the first examples of well-characterized isocyanide complexes of zinc. The X-ray structure of 4 showed that it is monomeric with a distorted tetrahedral coordination geometry of the metal centre, which reflects the steric requirements of the chalcogenolato and isocyanide ligands, respectively. 相似文献
13.
MoO 2(C 5H 7O 2) 2, where C 5H 7O 2 is 2,4-pentanedione (acac), reacts with 2-2′ pyridylbenzoxazole in acetone to give a product with stoichiometry, Mo 3C 24H 16N 6O 12. This product dissolves readily in dimethylformamide to give a brown solution which on standing for several weeks yielded crystals. An X-ray structure determination showed these crystals to contain uncoordinated 2-2′pyridylbenzoxazole and [(CH 3) 2NH 2] 4+[Mo 8O 26] 4−. 相似文献
14.
Reaction of potassium 3{5}-(3′,4′-dimethoxyphenyl)pyrazolide with 2-bromopyridine in diglyme at 130°C for 3 days followed by an aqueous quench, affords 1-{pyrid-2-yl}-3-{3′,4′-dimethoxyphenyl}pyrazole (L 2) in 69% yield after recrystallization from hot hexanes. Complexation of [Cu(NCMe) 4]BF 4 by 2 molar equivalents of 1-{pyrid-2-yl}-3-{2′,5′-dimethoxyphenyl}pyrazole (L 1) or L 2 in MeCN at room temperature, followed by concentration and crystallisation with Et 2O, gives [Cu(L) 2]BF 4 L = L 1, L 2) in good yields. Treatment of AgBF 4 with L 1 or L 2 in MeNO 2 similarly gives [Ag(L) 2]BF 4 L = L 1, L 2); reaction of AfBF 4 with L 2 in MeCN gives a product of stoichiometry [Ag(L 2)(NCMe)]BF 4. The 1H NMR spectra of the [M(L) 2]BF 4 complexes show peaks arising from a single coordinated environment. The single crystal X-ray structure of [Cu(L 1) 2]BF 4 shows a tetrahedral complex cation with Cu---N = 2.011(8), 2.036(8), 2.039(8), 2.110(8) Å. The Cu I centre is close to tetrahedral, the dihedral angle between the least-squares planes formed by the Cu atom and the N donor atoms of the two ligands being 88.3(3)°. Complexation of hydrated Cu(BF 4) 2 by L 2 in MeCN at room temperature yields [Cu(L 2) 2](BF 4) 2. The cyclic voltammograms of the three Ag I complexes in MeCN/0.1 M Bu 4n NPF 6 are suggestive of extensive ligand dissociation in this solvent. 相似文献
15.
The nature of the 8-quinolinato ligand in various forms has been examined by 15N, 13C and 119Sn NMR spectroscopy, with evidence also from electronic spectroscopy. These forms include 8-quinolinol (HQ), 8-quinolinate, the 8-hydroxyquinolinium ion, O- and N-methyl derivatives, 8-methoxyquinoline (MeQ), the zwitterionic N-methylquinolinium-8-olate and the N-methylquinolinium ion, and the chelating ligand in organotin(IV) complexes. The 15N shift from MeQ to HQ affords a measure of the intramolecular hydrogen bonding in HQ. The 15N shifts and 2J( 15N 1H) couplings afford criteria of chelation, and the O- and N-methyl compounds provide useful reference points for its assessment. Evidence for chelation is demonstrated in three groups of compounds, [SnR 2Q 2] (R = Me, Et, Bu n, Oct n or Ph), [SnR 3Q] (R = Me, Et, Bu n or Ph) and [SnR 2ClQ] (R = Me, Et, Bu n or Oct n), the 15N and 119Sn shielding increasing from the [SnR 3Q] to the [SnR 2Q 2] compounds. 相似文献
16.
The phosphorus azide [P(O 2C 12H 8)(N 3)] [(O 2C 12H 8) = 2,2′-dioxy-1,1′-biphenyl] undergoes a solid state polymerization at 30 °C giving a separable mixture of the polyphosphazene {[NP(O 2C 12H 8)]} n with a Mw in the range of 10 4, together with a fraction of small and large cyclic spirophosphazene oligomers {[NP(O 2C 12H 8)]} n, and an insoluble polymeric material with a very high char forming tendency, consisting very likely on a network of large interlooped cyclic oligomers and polymers of overall composition [NP(O 2C 12H 8)] n. The reaction proceeds with smooth though irregular release of nitrogen at first but tending to abrupt accelerations ending in an explosion. The later outcome is more likely in scales of 10–50 g, and results in a decrease in the yield of the soluble polymer and a large increase in the yield of the polymeric matrix. 相似文献
17.
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
18.
Trifunctional primary phosphines of the type 1,3,5-[PH 2(CH 2) n] 3C 6H 3 (3b–d) were obtained via an Arbusov reaction between the 1,3,5-tris(bromoalkyl)benzenes 1b–d and P(OEt) 3 followed by a reaction of the trisphosphonates 1,3,5-[(EtO) 2P(O)(CH 2) n] 3C 6H 3 (2b–d) with LiAlH 4. A straightforward conversion of these sensitive key phosphines 3b–d to the corresponding water-soluble ligands 1,3,5-tris[bis(hydroxymethyl)phosphinylalkyl]benzenes 4b–d and 1,3,5-tris[bis(2′-diethylphosphonatoethyl)phophinylalkyl]benzenes 5b–d was achieved by formylation with formaldehyde and hydrophosphonation with diethyl vinylphosphonate, respectively. A five component self-assembly consisting of three equivalents of the platinum(II) complex Cl 2Pt(NCPh) 2 and two equivalents of the ligands 5b–d under high dilution conditions resulted in the formation of the nanoscaled, water-soluble triplatinacyclophanes 6b–d in high yields. However, comparable reactions with the ligands 4b–d led only to polymeric materials, which are insoluble in all organic solvents and water. The structures of the metallacyclophanes 6b–d were elucidated by 31P{ 1H}-, 13C{ 1H}-, and 195Pt{ 1H}-NMR spectroscopic investigations. 相似文献
19.
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
20.
139La-NMR chemical shifts were measured for several anionic complexes of formulae Li(C 4H 8O 2) 3/2 [La(ν 3-C 3H 5) 4], [Li(C 4H 8O 2) 2][Cp′ nLa(ν 3-C 3]H 5) 4−n] (Cp′ = Cp(ν 5-C 5H 5); n = 1, 2 and Cp′ = Cp * (ν 5-C 5Me5); N = 1) and Li[R nLa(ν 3-C 3H 4) 4− n] (R = N(SiMe 3) 2; n = 1, 2 and R = CCsIMe 3; n = 4), as well as for neutral compounds for formulae La(ν 3-C 3H 5) 3L n (L = (C 4H 8O 2) 1.5, (HMPT) 2, TMED), Cp′ nLa(ν 3-C 3H 5) 3−n (Cp′= Cp(ν 5-Cp 5H 5), Cp *(ν 5-C 5Me 5); n = 1, 2) and La(ν 3-C 3H 2) 2X(THF) 2 X = Cl, Br, I). Typical ranges of the 139La-NMR chemical shifts were found for the different types of complex independent of number and kind of organyl groups directly bonded to lanthanum. Zusammenfassung139La-NMR-Spektroskopie wurde an einer Reihe anionischer Allyllanthanat(III)-Komplexe der Zusammensetzung
]- [La)ν3-C3H5)4, [Li(C4H8)2][Cp′nLa(ν3-C3H5)4−n(Cp′ = Cp(ν5-C5H5); n = 1, 2 und Cp′ = Cp * (ν5-C5Me5); N = 1) und Li[RnLa(ν3-C3H5)4−n (R = B(SiMe3)2; n = 1, 2 und R = CCSiMe3; n = 4 sowie neutraler Allyllanthan(III)-Komplexe der Zusammensetzung La(ν3-C3H5)3Ln (Ln = (C4H8O2)1.5, (HMPT)2, TMED), Cp′n, La(ν3-C3H5)3−n (Cp′ = Cp(ν5-C5H5), Cp * (ν5- Cp5Me5); n = 1, 2) und La(ν3-Cp3H5)2X(THF)2 (X = Cl, Br, I) durchgefürt. In Abhängikeit von der Anzahl und der Art der am Lanthan gebundenen Gruppen wurden für die verschieden Komplextypen charakteristische Resonanzbereiche ermittelt. 相似文献
|