共查询到20条相似文献,搜索用时 421 毫秒
1.
The reactions of anhydrous LnCl 3 (Ln = Nd or Lu) with three equivalents of {(Me 3Si) 2NC(NR) 2}Li (R = Pr i or Cy; Cy is cyclohexyl) in THF afforded the corresponding tris(guanidinate) derivatives of lanthanides {(Me 3Si) 2NC(NR) 2} 3Ln (Ln = Nd, R = Pr i, ( 1); Ln = Lu, R = Cy ( 2)), which were isolated after the recrystallization from hexane in 82 and 88% yields, respectively. The complex {(Me 3Si) 2NC(NCy) 2} 2{HC(NCy) 2}Nd ( 3) containing two guanidinate ligands and one formamidinate ligand was isolated in attempting to synthesize the bis(guanidinate) borohydride derivative by the reaction of {(Me 3Si) 2NC(N-Cy) 2}Na with Nd(BH 4) 3(THF) 2 (in a molar ratio of 2: 1) in THF. This complex is apparently formed as a result of the fragmentation and redistribution of the guanidinate ligands. The X-ray diffraction study showed that in the crystalline state compounds 1– 3 are mononuclear complexes containing no coordinated Lewis bases. 相似文献
2.
The reaction of Gd(BH 4) 3(THF) 2 with two equivalents of sodium N,N′-dicyclohexyl- N″-bis(trimethylsilyl)guanidinate in THF followed by the treatment of the reaction product with 1,2-dimethoxyethane produced the monoguanidinate bis(borohydride) complex [(Me 3Si) 2NC(NCy) 2]Gd(BH 4) 2DME ( 1) (Cy is cyclohexyl). The treatment of the heterobimetallic samarium complex {(Me 3Si) 2NC(NPr i) 2} 2Sm(BH 4) 2Li(THF) 2, in which the lanthanide and lithium atoms are linked by two bridging borohydride groups, with 1,2-dimethoxyethane afforded the ionic complex [{(Me 3Si) 2NC(NPr i) 2} 2Sm(BH 4) 2] ?[Li(DME) 3] + ( 2). The structures of complexes 1 and 2 were established by X-ray diffraction. The [(Me 3Si) 2NC(NCy) 2] 2Ln(BH 4) 2Li(THF) 2 complexes (Ln = Nd ( 3), Sm ( 4), or Yb ( 5)) were found to catalyze methyl methacrylate polymerization. 相似文献
3.
The mono(guanidinate) lanthanide borohydride complexes of [(Me 3Si) 2NC(NCy) 2]Ln(BH 4) 2(THF) 2 (Ln = Yb ( 1), Er ( 2)) have been synthesized by the reactions of corresponding Ln(BH 4) 3(THF) 3 with sodium guanidinate of [(Me 3Si) 2NC(NCy) 2]Na in a 1:1 molar ratio in THF. They were characterized by elemental analysis, infrared spectrum and X-ray diffraction analysis. 1 and 2 have similar structures. The lanthanide ion was bonded by an η 2-guanidinate ligand, two η 3-BH 4 ligands and two THF molecules as a distorted octahedron. The two BH 4 ligands in a complex are equivalent and cis to each other. The structure of solvated sodium guanidinate of {[(Me 3Si) 2NC(NCy) 2]Na(THF)} 2 ( 3) was also presented. In a dimeric molecule of 3, each Na atom is bound to three nitrogen atoms from two guanidinate groups and one oxygen atom from the THF molecule. 1 and 2 displayed moderate high catalytic activity for the polymerization of methyl methacrylate. The Er complex is more active than the Yb complex. 相似文献
4.
The “masked” terminal Zn sulfide, [K(2.2.2‐cryptand)][ MeLZn(S)] ( 2 ) ( MeL={(2,6‐ iPr 2C 6H 3)NC(Me)} 2CH), was isolated via reaction of [ MeLZnSCPh 3] ( 1 ) with 2.3 equivalents of KC 8 in THF, in the presence of 2.2.2‐cryptand, at ?78 °C. Complex 2 reacts readily with PhCCH and N 2O to form [K(2.2.2‐cryptand)][ MeLZn(SH)(CCPh)] ( 4 ) and [K(2.2.2‐cryptand)][ MeLZn(SNNO)] ( 5 ), respectively, displaying both Brønsted and Lewis basicity. In addition, the electronic structure of 2 was examined computationally and compared with the previously reported Ni congener, [K(2.2.2‐cryptand)][ tBuLNi(S)] ( tBuL={(2,6‐ iPr 2C 6H 3)NC( tBu)} 2CH). 相似文献
5.
The “masked” terminal Zn sulfide, [K(2.2.2-cryptand)][ MeLZn(S)] ( 2 ) ( MeL={(2,6- iPr 2C 6H 3)NC(Me)} 2CH), was isolated via reaction of [ MeLZnSCPh 3] ( 1 ) with 2.3 equivalents of KC 8 in THF, in the presence of 2.2.2-cryptand, at −78 °C. Complex 2 reacts readily with PhCCH and N 2O to form [K(2.2.2-cryptand)][ MeLZn(SH)(CCPh)] ( 4 ) and [K(2.2.2-cryptand)][ MeLZn(SNNO)] ( 5 ), respectively, displaying both Brønsted and Lewis basicity. In addition, the electronic structure of 2 was examined computationally and compared with the previously reported Ni congener, [K(2.2.2-cryptand)][ tBuLNi(S)] ( tBuL={(2,6- iPr 2C 6H 3)NC( tBu)} 2CH). 相似文献
6.
Treatment of LnCl 3 with [(SiMe 3) 2NC(N iPr) 2]Li in 1:2 molar ratio afforded the soluble bis(guanidinate)lanthanide chlorides {[(SiMe 3) 2NC(N iPr) 2] 2Ln(μ-Cl)} 2 (Ln=Y ( 1), Nd ( 2)). Amination of 1 and 2 with two equivalents of LiN( iPr) 2 in a mixture solution of toluene and hexane gave [(SiMe 3) 2NC(N iPr) 2] 2LnN( iPr) 2 (Ln=Y ( 3), Nd ( 4)) in good isolated yields. The single-crystal structural analyses of 2 and 3 revealed that the coordination geometries of lanthanide metals are best described as a distorted pseudo-octahedron and a pseudo-pyramid, respectively. Complexes 3 and 4 exhibited extremely high activity for the polymerizations of ε-caprolactone and methyl methacrylate (MMA). 相似文献
7.
The reaction of [(η 5-R 2PC 5H 4) 2Co][PF 6] with (Me 2S)AuCl (1:2) resulted in {[(η 5-R 2PC 5H 4) 2Co](AuCl) 2}[PF 6] (R = Ph, Cy, or
i
Pr). With a 1:1 ratio of [(η 5-R 2PC 5H 4)Co(η 5-C 5H 5)][PF 6] to (Me 2S)AuCl, yellow crystalline {[(η 5-R 2PC 5H 4)Co(η 5-C 5H 5)](AuCl)}[PF 6] was produced. The reaction of {[(η 5-Cy 2PC 5H 4)Co(η 5-C 5H 5)](AuCl)}[PF 6] with phenyl acetylene gave {[(η 5-Cy 2PC 5H 4)Co(η 5-C 5H 5)][Au(C≡C–Ph)]}[PF 6], while the reaction of {[(η 5-Cy 2PC 5H 4) 2Co](AuCl) 2}[PF 6] with phenyl acetylene produced the unusual ionic complex {[(η 5-Cy 2PC 5H 4) 2Co][Au(C≡C–Ph)] 2}[Au(C≡C–Ph) 2]. The structure of this complex has been characterized by X-ray crystallography, and a possible pathway for its formation
is suggested.
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. 相似文献
8.
The reactions of lanthanide tris(borohydrides) Ln(BH 4) 3(thf) 3 (Ln = Sm or Nd) with 2 equiv. of lithium N,N′-diisopropyl- N′-bis(trimethylsilyl)guanidinate in toluene produced the [(Me 3Si) 2NC(NPr i) 2]Ln(BH 4) 2Li(thf) 2 complexes (Ln = Sm or Nd), which were isolated in 57 and 42% yields, respectively, by recrystallization from hexane. X-ray
diffraction experiments and NMR and IR spectroscopic studies demonstrated that the reactions afford monomeric ate complexes, in which the lanthanide and lithium atoms are linked to each other by two bridging borohydride groups. The complexes
exhibit catalytic activity in polymerization of methyl methacrylate.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 441–445, March, 2007. 相似文献
9.
The hydrogenolysis of mono- and dinuclear Pd II hydroxides was investigated both experimentally and computationally. It was found that the dinuclear μ-hydroxide complexes {[(PCN R)Pd] 2(μ-OH)}(OTf) (PCN H=1-[3-[(di- tert-butylphosphino)methyl]phenyl]-1 H-pyrazole; PCN Me=1-[3-[(di- tert-butylphosphino)methyl]phenyl]-5-methyl-1 H-pyrazole) react with H 2 to form the analogous dinuclear hydride species {[(PCN R)Pd] 2(μ-H)}(OTf). The dinuclear μ-hydride complexes were fully characterized, and are rare examples of structurally characterized unsupported singly bridged μ-H Pd II dimers. The {[(PCN Me)Pd] 2(μ-OH)}(OTf) hydrogenolysis mechanism was investigated through experiments and computations. The hydrogenolysis of the mononuclear complex (PCN H)Pd-OH resulted in a mixed ligand dinuclear species [(PCN H)Pd](μ-H)[(PCC)Pd] (PCC=a dianionic version of PCN H bound through phosphorus P, aryl C, and pyrazole C atoms) generated from initial ligand “rollover” C−H activation. Further exposure to H 2 yields the bisphosphine Pd 0 complex Pd[(H)PCN H] 2. When the ligand was protected at the pyrazole 5-position in the (PCN Me)Pd−OH complex, no hydride formed under the same conditions; the reaction proceeded directly to the bisphosphine Pd 0 complex Pd[(H)PCN Me] 2. Reaction mechanisms for the hydrogenolysis of the monomeric and dimeric hydroxides are proposed. 相似文献
10.
Abstract The in vitro activity of a series of ruthenium clusters, [(η 6-C 6H 6)(η 6-C 6Me 6) 2Ru 3(μ-H) 3(μ 3-O)][BF 4], [(η 6-C 6H 6)(η 6-1,4- iPrC 6H 4Me)(η 6-C 6Me 6)Ru 3(μ-H) 3(μ 3-O)][BF 4], [(η 6-C 6H 6) 4Ru 4(μ-H) 4][BF 4] 2, [(η 6-C 6H 5Me) 4Ru 4(μ-H) 4][BF 4] 2 and [(η 6-C 6H 6) 4Ru 4(μ-H) 3(μ-OH)][Cl] 2, has been evaluated against A2780 and A2780cisR ovarian carcinoma cell lines. Both triruthenium clusters are very active
compared to ruthenium compounds in general, whereas the tetraruthenium clusters do not display significant cytotoxicities.
Since the triruthenium clusters are known to form supramolecular interactions with arenes and other functions, it is possible
that such interactions are also important with respect to their mode of biological activity. The X-ray structure analysis
of [(η 6-C 6H 5Me) 4Ru 4(μ-H) 4][PF 6] 2 is also reported.
Graphical Abstract The in vitro activity of a series of ruthenium clusters has been evaluated against A2780 and A2780cisR ovarian carcinoma cell lines and
their activity compared to cisplatin. The triruthenium clusters are very active, while the tetraruthenium clusters do not
display significant cytotoxicities.
Dedicated to Professor Dieter Fenske on the occasion of his 65th birthday anniversary 相似文献
11.
The reaction of Ru 3(CO) 12 with tetramethyltrifluoromethylcyclopentadiene at various ratios of the reagents was studied. Refluxing of Ru 3(CO) 12 with a sixfold excess of tetramethyltrifluoromethylcyclopentadiene in octane in an inert atmosphere gave a complex, which
is, according to X-ray diffraction data, a dimer, trans-[Ru(η 5-C 5Me 4CF 3)(CO) 2] 2. The reaction under the same conditions but starting from Ru 3(CO) 12 and C 5Me 4CF 3H in 2∶1 molar ratio gave a hexaruthenium cluster [Ru 6(μ 3-H)(η 2-μ 4-CO) 2(μ-CO)(Co) 12(η 5-C 5Me 4CF 2)], which was characterized by IR as well as 1H, 13C, and 19F NMR spectroscopy. According to X-ray diffraction data, an Ru 4 tetrahedron, in which two edges are bound by additional “briding” Ru atoms, constitutes the frame of this compound. This
complex has one (η 5-C 5Me 4CF 3) ligand, as well as one (μ 3-H) and two (η 2-μ 4-CO) groups.
Translated from Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 507–512, March, 1998. 相似文献
12.
The current library of amidinate ligands has been extended by the synthesis of two novel dimethylamino-substituted alkynylamidinate anions of the composition [Me 2N−CH 2−C≡C−C(NR) 2] − (R = iPr, cyclohexyl (Cy)). The unsolvated lithium derivatives Li[Me 2N−CH 2−C≡C−C(NR) 2] ( 1 : R = iPr, 2 : R = Cy) were obtained in good yields by treatment of in situ-prepared Me 2N−CH 2−C≡C−Li with the respective carbodiimides, R−N=C=N−R. Recrystallization of 1 and 2 from THF afforded the crystalline THF adducts Li[Me 2N−CH 2−C≡C−C(NR) 2] ⋅ nTHF ( 1 a : R = iPr, n=1; 2 a : R = Cy, n=1.5). Precursor 2 was subsequently used to study initial complexation reactions with selected di- and trivalent transition metals. The dark red homoleptic vanadium(III) tris(alkynylamidinate) complex V[Me 2N−CH 2−C≡C−C(NCy) 2] 3 ( 3 ) was prepared by reaction of VCl 3(THF) 3 with 3 equiv. of 2 (75 % yield). A salt-metathesis reaction of 2 with anhydrous FeCl 2 in a molar ratio of 2 : 1 afforded the dinuclear homoleptic iron(II) alkynylamidinate complex Fe 2[Me 2N−CH 2−C≡C−C(NCy) 2] 4 ( 4 ) in 69 % isolated yield. Similarly, treatment of Mo 2(OAc) 4 with 3 or 4 equiv. of 2 provided the dinuclear, heteroleptic molybdenum(II) amidinate complex Mo 2(OAc)[Me 2N−CH 2−C≡C−C(NCy) 2] 3 ( 5 ; yellow crystals, 50 % isolated yield). The cyclohexyl-substituted title compounds 2 a , 4 , and 5 were structurally characterized through single-crystal X-ray diffraction studies. 相似文献
13.
The reaction of [(MenacnacDipp)Mn(μ-Cl)]2(2) (MenacnacDipp = HC(C(Me)NDipp)2; Dipp = 2,6-Pri2C6H3) with sodium triethylborohydride in a toluene—THF mixture afforded the complex [(MenacnacDipp)Mn(μ-H)2BEt2(THF)] (3). The reaction of 2 with Na[HBEt3] in toluene under THF-free conditions gave a mixture of products. The set and the ratio of these products in the resulting crystalline mixture were established by quantitative powder X-ray diffraction analysis: [(MenacnacDipp)Mn(μ-H)]2(1), [(MenacnacDipp)?Mn(μ-H)2BEt2] (4), and unreacted compound 2 in the ratio of 15:4:1 and traces of an unknown crystalline phase. The reaction of [(MenacnacDipp)VCl2] (5) with Na[HBEt3] yielded the compound [(MenacnacDipp)V(μ-H)(μ,κ1:1?C:C′?C2H4)BEt2] (6) containing the unusual ligand [HBEt2(CH2CH2)]2?. The vanadium analog of compound 3, [(MenacnacDipp)V(μ-H)2BEt2(THF)] (7), was isolated in one experiment. Besides. a small amount of the complex [(MenacnacDipp)V(μ-H)BEt3(THF)] (8) was detected in the mixture of crystalline products. The structures of compounds 3, 4, 6, 7, and 8 were determined by single-crystal X-ray diffraction. 相似文献
14.
The reactions of mass-selected [CH 3NH 2] +˙ ions with the isomeric butenes and pentenes were studied at low collision energies in the radiofrequency-only quadrupole collision cell of a hybrid BEqQ tandem mass spectrometer. Characteristic iminium ions arising by addition of the methylamine to the olefin followed by fragmentation are observed for but-1-ene pent-1-ene and 3-methylbut-1-ene. However, for but-2-ene pent-2-ene 2-methylpropene 2-methylbut-1-ene and 2-methylbut-2-ene the major reaction channel of [CH 3NH 2] +˙ is charge exchange to form the olefinic molecular ion. The isomeric olefins are characterized to a considerable extent by the characteristic ion–molecule reactions that these molecular ions undergo with the neutral olefin. 相似文献
15.
Bis(dialkylamino)carbenium salts {[(Me 2N) 2CCl] +} 2MCl 4
2− (M=Ni, Pd) and {[Me 2NC(X)NR 2] +} 2PtCl 6
2− (R=Me, All; X=H, Cl, Me) are efficient catalysts for hydrosilylation of allyl phenyl ether, triallylamine, allyl chloride,
allylamine, and 1-octene with various hydrosilanes. The catalytic activity is dependent on the salt composition and the nature
of the metal M, the saturated compound, and the hydrosilane used. The catalysts used are usually insoluble in the reaction
mixture, active, and stable. In some cases, carbenium salts are more selective than Speier's catalyst. Novel catalysts, silica-immobilized
dialkylaminocarbenium salts, have been prepared. The kinetics of the reaction have been considered.
Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 5, pp. 1041–1044, May, 1997. 相似文献
16.
The limits of steric crowding in organometallic metallocene complexes have been examined by studying the synthesis of [(C 5Me 5) 3ML n] complexes as a function of metal in which L=Me 3CCN, Me 3CNC, and Me 3SiCN. The bis( tert‐butyl nitrile) complexes [(C 5Me 5) 3Ln(NCCMe 3) 2] (Ln=La, 1 ; Ce, 2 ; Pr, 3 ) can be isolated with the largest lanthanide metal ions, La 3+, Ce 3+, and Pr 3+. The Pr 3+ ion also forms an isolable mono‐nitrile complex, [(C 5Me 5) 3Pr(NCCMe 3)] ( 4 ), whereas for Nd 3+ only the mono‐adduct [(C 5Me 5) 3Nd(NCCMe 3)] ( 5 ) was observed. With smaller metal ions, Sm 3+ and Y 3+, insertion of Me 3CCN into the M? C(C 5Me 5) bond was observed to form the cyclopentadiene‐substituted ketimide complexes [(C 5Me 5) 2Ln{NC(C 5Me 5)(CMe 3)}(NCCMe 3)] (Ln=Sm, 6 ; Y, 7 ). With tert‐butyl isocyanide ligands, a bis‐isocyanide product can be isolated with lanthanum, [(C 5Me 5) 3La(CNCMe 3) 2] ( 8 ), and a mono‐isocyanide product with neodymium, [(C 5Me 5) 3Nd(CNCMe 3)] ( 9 ). Silicon–carbon bond cleavage was observed in reactions between [(C 5Me 5) 3Ln] complexes and trimethylsilyl cyanide, Me 3SiCN, to produce the trimeric cyanide complexes [{(C 5Me 5) 2Ln(μ‐CN)(NCSiMe 3)} 3] (Ln=La, 10 ; Pr, 11 ). With uranium, a mono‐nitrile reaction product, [(C 5Me 5) 3U(NCCMe 3)] ( 12 ), which is analogous to 5 , was obtained from the reaction between [(C 5Me 5) 3U] and Me 3CCN, but [(C 5Me 5) 3U] reacts with Me 3CNC through C? N bond cleavage to form a trimeric cyanide complex, [{(C 5Me 5) 2U(μ‐CN)(CNCMe 3)} 3] ( 13 ). 相似文献
17.
The reaction of anhydrous SmCl 3 with two equivalents of lithium N,N′-diisopropyl- N″-bis(trimethylsilyl)guanidinate in THF afforded the [{(Me 3Si) 2NC(NPr i) 2} 2SmCl] 2 complex ( 1) in 82% yield. Analogous reactions with YCl 3 and GdCl 3 produced the ate-complexes { (Me 3Si) 2NC(NPr i) 2} 2Ln(µ-Cl) 2Li(THF) 2 (Ln = Y ( 2) and Gd ( 3)). The structures of complexes 1 and 2 were established by X-ray diffraction. The reaction of complex 1 with NaBH 4 in hexane (20 °C) followed by treatment with dimethoxyethane yielded the unexpected product, { (Me 3Si) 2NC(NPr i) 2}Sm(µ 3-BH 4) 2(DME) ( 5). X-ray diffraction study showed that both borohydride ligands in complex 5 are tridentate. 相似文献
18.
The preparation and characterization of a series of neutral rare‐earth metal complexes [Ln(Me 3TACD)(η 3‐C 3H 5) 2] (Ln=Y, La, Ce, Pr, Nd, Sm) supported by the 1,4,7‐trimethyl‐1,4,7,10‐tetraazacyclododecane anion (Me 3TACD ?) are reported. Upon treatment of the neutral allyl complexes [Ln(Me 3TACD)(η 3‐C 3H 5) 2] with Brønsted acids, monocationic allyl complexes [Ln(Me 3TACD)(η 3‐C 3H 5)(thf) 2][B(C 6X 5) 4] (Ln=La, Ce, Nd, X=H, F) were isolated and characterized. Hydrogenolysis gave the hydride complexes [Ln(Me 3TACD)H 2] n (Ln=Y, n=3; La, n=4; Sm). X‐ray crystallography showed the lanthanum hydride to be tetranuclear. Reactivity studies of [Ln(Me 3TACD)R 2] n (R=η 3‐C 3H 5, n=0; R=H, n=3,4) towards furan derivatives includes hydrosilylation and deoxygenation under ring‐opening conditions. 相似文献
19.
The ring‐opening polymerization of trimethylene carbonate (TMC) using homoleptic lanthanide guanidinate complexes [RNC(NR′ 2)NR] 3Ln as single component initiators has been fully investigated for the first time. The substituents on guanidinate ligands and center metals show great effect on the catalytic activities of these complexes, that is, ? N(CH 2) 5 > ? N iPr 2 > ? NPh 2 (for R′), ? Cy > ? iPr (for R), and Yb > Sm > Nd. Among them, [Ph 2NC(NCy) 2] 3Yb shows the highest catalytic activity. Some features and kinetic behaviors of the TMC polymerization initiated by [Ph 2NC(NCy) 2] 3Yb were studied in detail. The polymerization rate is first order, with the monomer concentration and Mn of the polymer increasing with the polymer yield increasing linearly. The results indicated the present system having “living character.” A mechanism that the polymerization occurs via acyl‐oxygen bond cleavage rather than alkyl‐oxygen bond cleavage was proposed. The copolymerization of TMC with ?‐caprolactone (ε‐CL) initiated by [Ph 2NC(NCy) 2] 3Yb was also tested. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1778–1786, 2005 相似文献
20.
The reactions of [Ru(N 2)(PR 3)(‘N 2Me 2S 2’)] [‘N 2Me 2S 2’=1,2‐ethanediamine‐ N, N′‐dimethyl‐ N, N′‐bis(2‐benzenethiolate)(2?)] [ 1 a (R= iPr), 1 b (R=Cy)] and [μ‐N 2{Ru(N 2)(P iPr 3)(‘N 2Me 2S 2’)} 2] ( 1 c ) with H 2, NaBH 4, and NBu 4BH 4, intended to reduce the N 2 ligands, led to substitution of N 2 and formation of the new complexes [Ru(H 2)(PR 3)(‘N 2Me 2S 2’)] [ 2 a (R= iPr), 2 b (R=Cy)], [Ru(BH 3)(PR 3)(‘N 2Me 2S 2’)] [ 3 a (R= iPr), 3 b (R=Cy)], and [Ru(H)(PR 3)(‘N 2Me 2S 2’)] ? [ 4 a (R= iPr), 4 b (R=Cy)]. The BH 3 and hydride complexes 3 a , 3 b , 4 a , and 4 b were obtained subsequently by rational synthesis from 1 a or 1 b and BH 3?THF or LiBEt 3H. The primary step in all reactions probably is the dissociation of N 2 from the N 2 complexes to give coordinatively unsaturated [Ru(PR 3)(‘N 2Me 2S 2’)] fragments that add H 2, BH 4?, BH 3, or H ?. All complexes were completely characterized by elemental analysis and common spectroscopic methods. The molecular structures of [Ru(H 2)(PR 3)(‘N 2Me 2S 2’)] [ 2 a (R= iPr), 2 b (R=Cy)], [Ru(BH 3)(P iPr 3)(‘N 2Me 2S 2’)] ( 3 a ), [Li(THF) 2][Ru(H)(P iPr 3)(‘N 2Me 2S 2’)] ([Li(THF) 2]‐ 4 a ), and NBu 4[Ru(H)(PCy 3)(‘N 2Me 2S 2’)] (NBu 4‐ 4 b ) were determined by X‐ray crystal structure analysis. Measurements of the NMR relaxation time T1 corroborated the η 2 bonding mode of the H 2 ligands in 2 a ( T1=35 ms) and 2 b ( T1=21 ms). The H,D coupling constants of the analogous HD complexes HD‐ 2 a ( 1J(H,D)=26.0 Hz) and HD‐ 2 b ( 1J(H,D)=25.9 Hz) enabled calculation of the H? D distances, which agreed with the values found by X‐ray crystal structure analysis ( 2 a : 92 pm (X‐ray) versus 98 pm (calculated), 2 b : 99 versus 98 pm). The BH 3 entities in 3 a and 3 b bind to one thiolate donor of the [Ru(PR 3)(‘N 2Me 2S 2’)] fragment and through a B‐H‐Ru bond to the Ru center. The hydride complex anions 4 a and 4 b are extremely Brønsted basic and are instantanously protonated to give the η 2‐H 2 complexes 2 a and 2 b . 相似文献
|