Metal versus ligand alkylation in the reactivity of the (bis-iminopyridinato)Fe catalyst

The alkylation of the Brookhart-Gibson {2,6-[2,6-(i-Pr)2PhN=C(CH3)]2(C5H3N)} FeCl2 precatalyst with 2 equiv of LiCH2Si(CH3)3 led to the isolation of several catalytically very active products depending on the reaction conditions. The expected dialkylated species {2,6-[2,6-(i-Pr)2PhN=C(CH3)]2}(C5H3N)Fe(CH2SiMe3)2 (2) was indeed the major component of the reaction mixture. However, other species in which alkylation occurred at the pyridine ring ortho position, {2,6-[2,6-(i-Pr)2PhN=C(CH3)]2-2-CH2SiMe3}(C5H3N)Fe(CH2SiMe3) (1), and at the imine C atom, {2-[2,6-(i-Pr)2PhN=C(CH3)]-6-[2,6-(i-Pr)2PhNC(CH3)(CH2 SiMe3)](C5H3N)}Fe(CH2SiMe3) (3), have also been isolated and fully characterized. In addition, deprotonation of the methyl-imino functions and formation of a new divalent Fe catalyst {[2,6-[2,6-(i-Pr)2PhN-C=(CH2)]2(C5H3N)}Fe(mu-Cl)Li(THF)3 (4) also occurred depending on the reaction conditions. In turn, the formation of 4 might trigger the reductive coupling of two units through the methyl-carbon wings. This process resulted in the one-electron reduction of the metal center, affording a dinuclear Fe(I) alkyl catalyst {[{[2,6-(i-Pr)2C6H5]N=C(CH3)}(C5H3N){[2,6-(i-Pr)26H5]N=CCH2}Fe(CH2SiMe3)]}2 (5). Different from other metal derivatives, complex 5 could not be prepared from the monodeprotonated version of the ligand. Its reaction with a mixture of FeCl2 and RLi afforded instead [{2,6-[2,6-(i-Pr)2PhN-C=(CH2)]2(C5H3N)}FeCH2Si(CH3)3][Li(THF)4] (6) which is also catalytically active. All of these high-spin species have been shown to have high catalytic activity for olefin polymerization, producing polymers of two distinct natures, depending on the formal oxidation state of the metal center.     

Bis(imino)pyridine ligand deprotonation promoted by a transient iron amide

Addition of 2 equiv of LiNMe(2) to the bis(imino)pyridine ferrous dichloride, ((i)(Pr)PDI)FeCl(2) ((i)(Pr)PDI = (2,6-(i)()Pr(2)-C(6)H(3)N=CMe)(2)C(5)H(3)N), resulted in deprotonation of the chelate methyl groups, yielding the bis(enamide)pyridine iron dimethylamine adduct, ((i)(Pr)PDEA)Fe(NHMe(2)) ((i)(Pr)PDEA = (2,6-(i)Pr(2)-C(6)H(3)NC=CH(2))(2)C(5)H(3)N). Performing a similar procedure with KN(SiMe(3))(2) in THF solution afforded the corresponding bis(THF) adduct, ((i)(Pr)PDEA)Fe(THF)(2). ((i)(Pr)PDEA)Fe(NHMe(2)) has also been prepared by addition of the free amine to the iron dialkyl complex, ((i)(Pr)PDI)Fe(CH(2)SiMe(3))(2), implicating formation of a transient iron amide that is sufficiently basic to deprotonate the bis(imino)pyridine methyl groups. Deprotonation of the amine ligand in ((i)(Pr)PDEA)Fe(NHMe(2)) has been accomplished by addition of amide bases to afford the ferrous amide-ate complexes, [((i)(Pr)PDEA)Fe(mu-NMe(2))M] (M = Li, K).     

Synthesis and electronic structure of cationic, neutral, and anionic bis(imino)pyridine iron alkyl complexes: evaluation of redox activity in single-component ethylene polymerization catalysts

A family of cationic, neutral, and anionic bis(imino)pyridine iron alkyl complexes has been prepared, and their electronic and molecular structures have been established by a combination of X-ray diffraction, Mo?ssbauer spectroscopy, magnetochemistry, and open-shell density functional theory. For the cationic complexes, [((iPr)PDI)Fe-R][BPh(4)] ((iPr)PDI = 2,6-(2,6-(i)Pr(2)-C(6)H(3)N═CMe)(2)C(5)H(3)N; R = CH(2)SiMe(3), CH(2)CMe(3), or CH(3)), which are known single-component ethylene polymerization catalysts, the data establish high spin ferrous compounds (S(Fe) = 2) with neutral, redox-innocent bis(imino)pyridine chelates. One-electron reduction to the corresponding neutral alkyls, ((iPr)PDI)Fe(CH(2)SiMe(3)) or ((iPr)PDI)Fe(CH(2)CMe(3)), is chelate-based, resulting in a bis(imino)pyridine radical anion (S(PDI) = 1/2) antiferromagnetically coupled to a high spin ferrous ion (S(Fe) = 2). The neutral neopentyl derivative was reduced by an additional electron and furnished the corresponding anion, [Li(Et(2)O)(3)][((iPr)PDI)Fe(CH(2)CMe(3))N(2)], with concomitant coordination of dinitrogen. The experimental and computational data establish that this S = 0 compound is best described as a low spin ferrous compound (S(Fe) = 0) with a closed-shell singlet bis(imino)pyridine dianion (S(PDI) = 0), demonstrating that the reduction is ligand-based. The change in field strength of the bis(imino)pyridine coupled with the placement of the alkyl ligand into the apical position of the molecule induced a spin state change at the iron center from high to low spin. The relevance of the compounds and their electronic structures to olefin polymerization catalysis is also presented.     

Synthesis and hydrogenation of bis(imino)pyridine iron imides

Treatment of the iron bis(dinitrogen) complex, (iPrPDI)Fe(N2)2 (iPrPDI = (2,6-iPr2C6H3N=CMe)2C5H3N), with a series of aryl azides resulted in loss of 3 equiv of N2 and formation of the corresponding four-coordinate iron imide compounds, (iPrPDI)Fe(NAr). These complexes, two of which (Ar = 2,6-iPr2-C6H3 and 2,4,6-Me3-C6H2) have been characterized by X-ray diffraction, are significantly distorted from planarity. The metrical parameters in combination with M?ssbauer spectroscopic and SQUID magnetic data suggest an intermediate spin iron(III) center antiferromagnetically coupled to a ligand-centered radical. Nitrene group transfer has been accomplished by addition of 1 atm of CO, yielding aryl isocyanates, ArNCO, and (iPrPDI)Fe(CO)2. Hydrogenation of the more sterically hindered members of the series furnished free aniline and the previously reported iron dihydrogen complex. Catalytic aryl azide hydrogenation has also been achieved, and the observed relative rates are consistent with N-H bond formation as the rate-determining step in aniline formation.     

Preparation and molecular and electronic structures of iron(0) dinitrogen and silane complexes and their application to catalytic hydrogenation and hydrosilation

Reduction of the five-coordinate iron(II) dihalide complexes (iPrPDI)FeX2 (iPrPDI = ((2,6-CHMe2)2C6H3N=CMe)2C5H3N; X = Cl, Br) with sodium amalgam under 1 atm of dinitrogen afforded the square pyramidal, high spin iron(0) bis(dinitrogen) complex (iPrPDI)Fe(N2)2. In solution, (iPrPDI)Fe(N2)2 loses 1 equiv of N2 to afford the mono(dinitrogen) adduct (iPrPDI)Fe(N2). Both dinitrogen compounds serve as effective precatalysts for the hydrogenation and hydrosilation of olefins and alkynes. Effecient catalytic reactions are observed with low catalyst loadings (< or = 0.3 mol %) at ambient temperature in nonpolar media. The catalytic hydrosilations are selective in forming the anti-Markovnikov product. Structural characterization of a high spin iron(0) alkyne and a bis(silane) sigma-complex has also been accomplished and in combination with isotopic labeling studies provides insight into the mechanism of both catalytic C-H and catalytic C-Si bond formation.     

亚胺膦亚胺型稀土双烷基配合物对丁二烯1,2-选择性聚合

以三烷基钪Sc(CH2SiMe3)3(THF)2和胺基膦亚胺配体为原料,经烷基消去反应合成了胺基膦亚胺(NPN)型配体螯合钪烷基配合物。 其结构用1H NMR、13C NMR、元素分析和X射线衍射分析进行了表征。 在助催化剂有机硼盐和烷基铝的作用下,该配合物对丁二烯聚合表现出了较高的催化活性。 并且随着聚合温度的降低,催化剂的1,2-选择性也随之升高。 聚合温度为-75 ℃时,产物的1,2-结构含量高达98.0%,聚合物的分子量为2.95×104,分子量分布为1.65。     

Synthetic and structural experiments on yttrium, cerium and magnesium trimethylsilylmethyls and their reaction products with nitriles; with a note on two cerium beta-diketiminates

The yttrium, cerium and magnesium bis(trimethylsilyl)methyls [Ln[CH(SiMe3)2]3][Ln = Y (1), Ce (2)], and the known compound Mg[[CH(SiMe3)2]2 (C) and [Mg(mu-Br)[CH(SiMe3)2](OEt2)]2 (D) formed the crystalline nitrile adducts [1(NCBut)2] (5), [2(NCPh)] (6), [C(NCR)2][R = But (8), Ph (9), C6H3Me2-2,6 (10)] and [Mg(mu-Br)[CH(SiMe3)2](NCR)]2 [R = But (11), Ph (12), C6H3Me2-2,6 (13)], rather than beta-diketiminato-metal insertion products. The beta-diketiminato-cerium complex [Ce[(N(SiMe3)C(C6H4But-4))2CH][N(SiMe3)2]2] (16) was obtained from [Ce[N(SiMe3)2]3] and the beta-diketimine H[[N(SiMe3)C(C6H4But-4)]2CH]]. The cerium alkyl 2 and [Ln[CH(SiMe3)(SiMe2OMe)]3][Ln = Y (3), Ce (4)] were obtained from the appropriate lithium alkyl precursor and [Ce(OC6H2But2-2,6-Me-4)3] or LnCl3, respectively. Heating complex 3 with benzonitrile in toluene afforded 2,2-dimethyl-4,6-diphenyl-5-trimethylsilyl-1,3-diaza-2-silahexa-1,3-diene (7), a member of a new class of heterocycles. The X-ray structures of the crystalline compounds, D, [Mg[CH(SiMe3)2]2(OEt2)2], the known [Ce(Cl)[(N(SiMe3)C(Ph))2CH]2] (E) and 16 are reported. The cerium alkyl (like 1) has one close Ce...C contact for each ligand, attributed to a gamma-C-Ce agostic interaction. The Ln alkyls and have a trigonal prismatic arrangement of the chelating ligands (each of the same chirality at Calpha) around the metal. In an arene solution at 313 K exists as two isomers, as evident from detailed NMR spectroscopic experiments.     

Solution structures and dynamic properties of chelated d(0) metal olefin complexes [eta(5): eta(1)-C(5)R(4)SiMe(2)N(t)Bu]Ti(OCMe(2)CH(2)CH(2)CH=CH(2))(+) (R = H, Me): Models for the [eta(5): eta(1)-C(5)R(4)SiMe(2)N(t)Bu]Ti(R')(olefin)(+) intermediates in "constrained geometry" catalysts.

To model the Ti-olefin interaction in the putative [eta(5): eta(1)-C(5)R(4)SiMe(2)N(t)Bu]Ti(R')(olefin)(+) intermediates in "constrained geometry" Ti-catalyzed olefin polymerization, chelated alkoxide olefin complexes [eta(5): eta(1)-C(5)R(4)SiMe(2)N(t)Bu]Ti(OCMe(2)CH(2)CH(2)CH=CH(2))(+) have been investigated. The reaction of [eta(5): eta(1)-C(5)R(4)SiMe(2)N(t)Bu]TiMe(2) (1a,b; R = H, Me) with HOCMe(2)CH(2)CH(2)CH=CH(2) yields mixtures of [eta(5)-C(5)R(4)SiMe(2)NH(t)Bu]TiMe(2)(OCMe(2)CH(2)CH(2)CH=CH(2)) (2a,b) and [eta(5): eta(1)-C(5)R(4)SiMe(2)N(t)Bu]TiMe(OCMe(2)CH(2)CH(2)CH=CH(2)) (3a,b). The reaction of 2a/3a and 2b/3b mixtures with B(C(6)F(5))(3) yields the chelated olefin complexes [[eta(5): eta(1)-C(5)R(4)SiMe(2)N(t)Bu]Ti(OCMe(2)CH(2)CH(2)CH=CH(2))][MeB(C(6)F(5))(3)] (4a,b; 71 and 89% NMR yield). The reaction of 2b/3b with [Ph(3)C][B(C(6)F(5))(4)] yields [[eta(5): eta(1)-C(5)Me(4)SiMe(2)N(t)Bu]Ti(OCMe(2)CH(2)CH(2)CH=CH(2))][B(C(6)F(5))(4)] (5b, 88% NMR yield). NMR studies establish that 4a,b and 5b exist as mixtures of diastereomers (isomer ratios: 4a/4a', 62/38; 4b/4b', 75/25; 5b/5b', 75/25), which differ in the enantioface of the olefin that is coordinated. NMR data for these d(0) metal olefin complexes show that the olefin coordinates to Ti in an unsymmetrical fashion primarily through C(term) such that the C=C pi bond is polarized with positive charge buildup on C(int). Dynamic NMR studies show that 4b/4b' undergoes olefin face exchange by a dissociative mechanism which is accompanied by fast inversion of configuration at Ti ("O-shift") in the olefin-dissociated intermediate. The activation parameters for the conversion of 4b to 4b' (i.e., 4b/4b' face exchange) are: DeltaH = 17.2(8) kcal/mol; DeltaS = 8(1) eu. 4a/4a' also undergoes olefin face exchange but with a lower barrier (DeltaH = 12.2(9) kcal/mol; DeltaS = -2(3) eu), for the conversion of 4a to 4a'.     

Reduction of carbodiimides by samarium(II) bis(trimethylsilyl)amides-formation of oxalamidinates and amidinates through C-C coupling or C-H activation

The reaction of [Sm{N(SiMe3)2}2(THF)2] (THF=tetrahydrofuran) with carbodiimides RN=C=NR (R=Cy, C6H3-2,6-iPr2) led to the formation of dinuclear SmIII complexes via differing C-C coupling processes. For R=Cy, the product [{(Me3Si)2N}2Sm(micro-C2N4Cy4)Sm{N(SiMe3)2}2] (1) has an oxalamidinate [C2N4Cy4]2- ligand resulting from coupling at the central C atoms of two CyNCNCy moieties. In contrast, for R=C6H3-2,6-iPr2, H transfer and an unusual coupling of two iPr methine C atoms resulted in a linked formamidinate complex, [{(Me3Si)2N}2Sm{micro-(RNC(H)N(Ar-Ar)NC(H)NR)}Sm{N(SiMe3)2}2] (2) (Ar-Ar=C6H3-2-iPr-6-C(CH3)2C(CH3)2-6'-C6H3-2'-iPr). Analogous reactions of RN=C=NR (R=Cy, C6H3-2,6-iPr2) with the SmII "ate" complex [Sm{N(SiMe2)3Na] gave 1 for R=Cy, but a novel C-substituted amidinate complex, [(THF)Na{N(R)C(NR)CH2Si(Me2)N(SiMe3)}Sm{N(SiMe3)2}2] (3), for R=C6H3-2,6-iPr2, via gamma C-H activation of a N(SiMe3)2 ligand.     

O(2) activation and hydrolysis of Salan rare-earth metal alkyl complexes

Salan ligated yttrium alkyl complex , L(1)Y(CH(2)SiMe(3))(THF) (Salan = L(1): [2-O-3,5-tBu(2)-C(6)H(2)CH(2)N(CH(3))CH(2)](2)), was exposed to an oxygen/nitrogen atmosphere to give a bimetallic alkoxide complex , [L(1)Y(mu-OCH(2)SiMe(3))](2). Whilst the lutetium counterparts (L(1)Lu(CH(2)SiMe(3))(THF)) and (L(2)Lu(CH(2)SiMe(3))(THF); L(2): [2-O-3-tBu-C(6)H(2)CH(2)N(CH(3))CH(2)](2)) were hydrolysed with moist nitrogen to afford mixed hydroxy/silyloxy complexes and ([L(1,2)Lu(mu-OSiMe(3))(mu-OH)LuL(1,2)]), respectively.     

Highly trans-1,4 selective (co-)polymerization of butadiene and isoprene with quinolyl anilido rare earth metal bis(alkyl) precursors

The N-R-quinolinyl-8-amino ligands HL(1-3) (R = 2,6-(i)Pr(2)C(6)H(3) (HL(1)), 2,6-Et(2)C(6)H(3) (HL(2)), 2,6-Me(2)C(6)H(3) (HL(3))) have been prepared, which reacted readily with one equiv. of rare earth metal tris(alkyl)s to afford the corresponding bis(alkyl) complexes L(1)Y(CH(2)SiMe(3))(2)(THF) (1) and L(1-3)Lu(CH(2)SiMe(3))(2)(THF) (2-4) via alkane elimination. Contrastingly, treatment of the in situ generated neodymium tri(alkyl)s with HL(1) afforded a mono(alkyl) neodymium complex (5). Complexes 1, 2 and 5 in combination with aluminium alkyls and organoborates established homogenous ternary systems that exhibited versatile catalytic activities and trans-1,4 selectivities for the polymerization of butadiene, depending on the types of aluminium alkyl, organoborate and rare earth metal used. Furthermore, the trans-1,4 selective copolymerization of butadiene and isoprene was achieved by using the ternary system of 1/AlMe(3)/[Ph(3)C][B(C(6)F(5))(4)]. Both the kinetics of copolymerization and the thermal behavior of the copolymers were investigated.     

Neutral and cationic alkylmanganese(II) complexes containing 2,6-bisiminopyridine ligands

Manganese alkyl complexes stabilised by 2,6-bis(N,N'-2,6-diisopropyl-phenyl)acetaldiminopyridine ((iPr)BIP) have been selectively prepared by reacting suitable alkylmanganese(II) precursors, such as homoleptic dialkyls [(MnR(2))(n)] or the corresponding THF adducts [{MnR(2)(thf)}(2)] with the mentioned ligand. For R=CH(2)CMe(2)Ph or CH(2)Ph, formally Mn(I) derivatives are produced, in which one of the two R groups migrates to the 4-position of the central pyridine ring in the (iPr)BIP ligand. In contrast, a true dialkyl complex [MnR(2)((iPr)BIP)] can be isolated for R=CH(2)SiMe(3). In solution, this compound slowly evolves to the corresponding Mn(I) monoalkyl derivative. A detailed study of this reaction provides insights on its mechanism, showing that it proceeds through successive alkyl migrations, followed by spontaneous dehydrogenation. Protonation of [Mn(CH(2)SiMe(3))(2)((iPr)BIP)] with the pyridinium salt [H(Py)(2)][BAr'(4)] (Ar'=3,5-C(6)H(3)(CF(3))(2)) leads to the cationic species [Mn(CH(2)SiMe(3))(Py)((iPr)BIP)](+). Alternatively, the same complex can be produced by reaction of the pyridine complex [{Mn(CH(2)SiMe(3))(2)(Py)}(2)] with the protonated ligand salt [H(iPr)BIP](+)[BAr'(4)](-). This last reaction allows the synthesis of analogous cationic alkylmanganese(II) derivatives, when precursors of type [MnR(2)((iPr)BIP)] are not available. Treatment of these neutral and cationic (iPr)BIP alkylmanganese derivatives with a range of typical co-catalysts (modified methylaluminoxane (MMAO), B(C(6)F(5))(3), trimethyl or triisobutylaluminum) does not lead to active ethylene polymerisation catalysts.     

Iron-catalyzed [2pi + 2pi] cycloaddition of alpha,omega-dienes: the importance of redox-active supporting ligands

The bis(imino)pyridine iron bis(dinitrogen) complex, (iPrPDI)Fe(N2)2 (iPrPDI = 2,6-(2,6-iPr2C6H3NCR)2C5H3N), serves as an efficient precursor for the catalytic [2pi + 2pi] cycloaddition of alpha,omega-dienes to yield the corresponding bicycles. For amine substrates, the rate of catalytic turnover increases with the size of the nitrogen substituents, demonstrating competing heterocycle coordination and product inhibition. In one case, a bis(imino)pyridine iron azobicycloheptane product was characterized by X-ray diffraction. Preliminary mechanistic studies highlight the importance of the redox activity of the bis(imino)pyridine ligand to maintain the ferrous oxidation state throughout the catalytic cycle.     

Synthesis, structures and reactions of lithium complexes of [(o-RCHC6H4)PPh2=NSiMe3]-(R = H, SiMe3) ligands

N-Trimethylsilyl o-methylphenyldiphenylphosphinimine, (o-MeC6H4)PPh2=NSiMe3 (1), was prepared by reaction of Ph2P(Br)=NSiMe3 with o-methylphenyllithium. Treatment of 1 with LiBun and then Me3SiCl afforded (o-Me3SiCH2C6H4)PPh2=NSiMe3 (2). Lithiations of both 1 and 2 with LiBu(n) in the presence of tmen gave crystalline lithium complexes [Li{CH(R)C6H4(PPh(2=NSiMe3)-.tmen](3, R = H; 4, R = SiMe3). From the mother liquor of 4, traces of the tmen-bridged complex [Li{CH(SiMe3)C6H4(PPh2=NSiMe3)-2}]2(mu-tmen) (5) were obtained. Reaction of 2 with LiBun in Et2O yielded complex [Li{CH(SiMe3)C6H4(PPh2=NSiMe3)-2}.OEt2] (6). Reaction of lithiated with Me2SiCl2 in a 2:1 molar ratio afforded dimethylsilyl-bridged compound Me2Si[CH2C6H4(PPh2=NSiMe3)-2]2 (7). Lithiation of 7 with two equivalents of LiBun in Et2O yielded [Li2{(CHC6H4(PPh2=NSiMe3)-2)2SiMe2}.0.5OEt2](8.0.5OEt2). Treatment of 4 with PhCN formed a lithium enamide complex [Li{N(SiMe3)C(Ph)CHC6H4(PPh2=NSiMe3)-2}.tmen] (9). Reaction of two equivalents of 5 with 1,4-dicyanobenzene gave a dilithium complex [{Li(OEt2)2}2(1,4-{C(N(SiMe3)CHC6H4(PPh2=NSiMe3)-2}2C6H4)] (10). All compounds were characterised by NMR spectroscopy and elemental analyses. The structures of compounds 2, 3, 5, 6 and 9 have been determined by single crystal X-ray diffraction techniques.     

Cationic rare-earth metal trimethylsilylmethyl complexes supported by THF and 12-crown-4 ligands: synthesis and structural characterization

To expand the limited range of rare-earth metal cationic alkyl complexes known, a series of mono- and dicationic trimethylsilylmethyl complexes supported by THF and 12-crown-4 ligands with [BPh4]-, [BPh3(CH2SiMe3)]-, [B(C6F5)4]-, [B(C6F5)3(CH2SiMe3)]-, and [Al(CH2SiMe3)4]- anions were prepared from corresponding neutral precursors [Ln(CH2SiMe3)3Ln] (Ln = Sc, Y, Lu; L = THF, n = 2 or 3; L = 12-crown-4, n = 1) as solvent-separated ion pairs. The syntheses of the monocationic derivatives [Ln(CH2SiMe3)2(12-crown-4)n(THF)m]+[A]- are all high yielding and proceed rapidly in THF solution at room temperature. A "one pot" procedure using the neutral species directly for the syntheses of a number of lutetium and yttrium dicationic derivatives [Ln(CH2SiMe3)(12-crown-4)n(THF)m]2+[A]-2 with a variety of different anions, a class of compounds previously limited to just a few examples, is presented. When BPh3 is used to generate the ion triple, the presence of 12-crown-4 is required for complete conversion. Addition of a second equiv of 12-crown-4 and a third equiv of [NMe2PhH]+[B(C6F5)4]- abstracts a third alkyl group from [Ln(CH2SiMe3)(12-crown-4)2(THF)x]2+[B(C6F5)4]-2 (Ln = Y, Lu). X-ray crystallography and variable-temperature (VT) NMR spectroscopy reveal a structural diversity within the known series of neutral 12-crown-4 supported tris(trimethylsilylmethyl) complexes [Ln(CH2SiMe3)3(12-crown-4)] (Ln = Sc, Y, Sm, Gd-Lu) in the solid and solution states. The X-ray structure of [Sc(CH2SiMe3)3(12-crown-4)] exhibits incomplete 12-crown-4 coordination. VT NMR spectroscopy indicates fluxional 12-crown-4 coordination on the NMR time scale. X-ray crystallography of only the second structurally characterized dicationic rare-earth metal alkyl complex [Y(CH2SiMe3)(12-crown-4)(THF)3]2+[BPh4]-2 shows exocyclic 12-crown-4 coordination at the 8-coordinate metal center with well separated counteranions. 11B and 19F NMR spectroscopy of all mono- and dicationic rare-earth metal complexes reported demonstrate that the anions are symmetrical and noncoordinating on the NMR time scale. A series of trends within the 1H and 13C{1H} NMR resonances arising from the Ln-CH2 groups and, in the case of yttrium, the 1JYC coupling constants at the Y-CH2 group and the 89Y chemical shift values are discussed.     

Synthesis and Crystal Structure of Binuclear Copper （Ⅱ） Complex Containing （Dimethylaminomethyl）ferrocene

1 INTRODUCTION Transition metal complexes with ferrocene are of considerable interest in the past fifty years because of their novel structures and special properties[1, 2]. The chemistry of ferrocene and its derivatives has become richer and richer in the last decade. Many complexes containing ferrocenyl have been synthesized and characterized[3～5]. Recently we have reported the synthesis and crystal structure of dibromo[1,1?bis(diphenylphosphino)- ferrocene]cadmium (Ⅱ)[6]. Herein we…     

Synthesis and reactivity of mono(amidinate) organoiron(II) complexes

The mono(amidinate) iron(ii) ferrate complex [{PhC(NAr)(2)}FeCl(micro-Cl)Li(THF)(3)] (1, Ar = 2,6-iPr(2)C(6)H(3)) was prepared and was found to undergo ligand redistribution in non-coordinating solvents to give the homoleptic [{PhC(NAr)(2)}(2)Fe] (2) as the only isolable product. Reaction of with alkylating agents also induces this redistribution, but the presence of pyridine allows isolation of the four-coordinate 14 VE monoalkyl complex [{PhC(NAr)(2)}FeCH(2)SiMe(3)(py)] (4). Generation of the 12 VE alkyl via pyridine abstraction from 4 by B(C(6)F(5))(3) again induced ligand redistribution. Attempts to trap a 12 VE alkyl species with CO led to the isolation of a dimeric Fe(0)-Li-ferrate complex (3) with a carbamoyl ligand, derived from CO insertion into the iron-amidinate bond.     

Rare-earth-metal-hydrocarbyl complexes bearing linked cyclopentadienyl or fluorenyl ligands: synthesis, catalyzed styrene polymerization, and structure-reactivity relationship

A series of rare-earth-metal-hydrocarbyl complexes bearing N-type functionalized cyclopentadienyl (Cp) and fluorenyl (Flu) ligands were facilely synthesized. Treatment of [Y(CH(2)SiMe(3))(3)(thf)(2)] with equimolar amount of the electron-donating aminophenyl-Cp ligand C(5)Me(4)H-C(6)H(4)-o-NMe(2) afforded the corresponding binuclear monoalkyl complex [({C(5)Me(4)-C(6)H(4)-o-NMe(μ-CH(2))}Y{CH(2)SiMe(3)})(2)] (1a) via alkyl abstraction and C-H activation of the NMe(2) group. The lutetium bis(allyl) complex [(C(5)Me(4)-C(6)H(4)-o-NMe(2))Lu(η(3)-C(3)H(5))(2)] (2b), which contained an electron-donating aminophenyl-Cp ligand, was isolated from the sequential metathesis reactions of LuCl(3) with (C(5)Me(4)-C(6)H(4)-o-NMe(2))Li (1 equiv) and C(3)H(5)MgCl (2 equiv). Following a similar procedure, the yttrium- and scandium-bis(allyl) complexes, [(C(5)Me(4)-C(5)H(4)N)Ln(η(3)-C(3)H(5))(2)] (Ln=Y (3a), Sc (3b)), which also contained electron-withdrawing pyridyl-Cp ligands, were also obtained selectively. Deprotonation of the bulky pyridyl-Flu ligand (C(13)H(9)-C(5)H(4)N) by [Ln(CH(2)SiMe(3))(3)(thf)(2)] generated the rare-earth-metal-dialkyl complexes, [(η(3)-C(13)H(8)-C(5)H(4)N)Ln(CH(2)SiMe(3))(2)(thf)] (Ln=Y (4a), Sc (4b), Lu (4c)), in which an unusual asymmetric η(3)-allyl bonding mode of Flu moiety was observed. Switching to the bidentate yttrium-trisalkyl complex [Y(CH(2)C(6)H(4)-o-NMe(2))(3)], the same reaction conditions afforded the corresponding yttrium bis(aminobenzyl) complex [(η(3)-C(13)H(8)-C(5)H(4)N)Y(CH(2)C(6)H(4)-o-NMe(2))(2)] (5). Complexes 1-5 were fully characterized by (1)H and (13)C NMR and X-ray spectroscopy, and by elemental analysis. In the presence of both [Ph(3)C][B(C(6)F(5))(4)] and AliBu(3), the electron-donating aminophenyl-Cp-based complexes 1 and 2 did not show any activity towards styrene polymerization. In striking contrast, upon activation with [Ph(3)C][B(C(6)F(5))(4)] only, the electron-withdrawing pyridyl-Cp-based complexes 3, in particular scandium complex 3b, exhibited outstanding activitiy to give perfectly syndiotactic (rrrr >99%) polystyrene, whereas their bulky pyridyl-Flu analogues (4 and 5) in combination with [Ph(3)C][B(C(6)F(5))(4)] and AliBu(3) displayed much-lower activity to afford syndiotactic-enriched polystyrene.     

Hydrogenation of C=C and C=N Bonds of the Amide-Imine Ligand in the Metal Coordination Sphere in the Reaction of Yttrium Bis(alkyl) Complex [2,6-iso-Pr2C6H3NC(=CH2)C(Me)=NC6H3-iso-Pr2-2,6]Y(CH2SiMe3)2(THF) with Molecular Hydrogen

Russian Journal of Coordination Chemistry - On treatment of the yttrium bis(alkyl) complex [ArNC(=CH2)C(Me)=NAr]Y(CH2SiMe3)2(THF) (I, Ar = C6H3-iso-Pr2-2.6) containing an amide-imine ligand, with...     

Latent low-coordinate titanium imides supported by a sterically encumbering beta-diketiminate ligand

Addition of an equal molar quantity of R- (R = Me, SiMe3) to complex (Nacnac)Ti=NAr(OTf) (Nacnac- =[ArNC(tBu)]2CH, Ar = 2,6-iPr2C6H3) forms the imido alkyl (Nacnac)Ti=NAr(R), which can be readily protonated to afford [(Nacnac)Ti=NAr(L)]+ (L = THF, Et2O, eta1-C6H5NMe2), or treated with B(C6F5)3 to afford the zwitterion (Nacnac)Ti=NAr(micro-CH3)B(C6F5)3.