Alkali metal zincate reagents are attracting considerable attention at present in respect to their often special reactivity/selectivity in hydrogen-metal and halogen-metal interconversion reactions. Heteroleptic diorgano-amidozincates, typified by lithium di-tert-butyltetramethylpiperidinozincate, have proved to be especially useful reagents in such applications. In this paper the related sodium TMP-zincate, prepared as its TMEDA (N,N,N',N'-tetramethylethylenediamine) adduct, [TMEDA.Na(mu-tBu)(mu-TMP)Zn(tBu)], 1, is introduced. This new zincate was synthesized from a 1:1:1 mixture of tBu2Zn, NaTMP, and TMEDA in hexane solution, as a colorless crystalline solid in an isolated yield of 58%. It has been characterized in solution by 1H and 13C NMR spectroscopic studies. An X-ray crystallographic study reveals that 1 adopts a five-membered (NaNZnCC) ring system featuring a TMP bridge and an unusual, asymmetrical tBu bridge involving a Na...Me agostic contact. Probing the basicity of 1, reaction with benzene affords the new hetero(tri)leptic zincate [TMEDA.Na(mu-Ph)(mu-TMP)Zn(tBu)], 2, which has also been crystallographically characterized. Thus, in this hydrogen-metal exchange reaction 1 functions as an alkyl base, with the elimination of butane, as opposed to an amido base. Also reported are DFT calculations using B3LYP functionals and the 6-311G** basis set on model zincate systems, which intimate that the preference of 1 for tBu ligand transfer over TMP ligand transfer in the reaction toward benzene is due to favorable thermodynamic factors.

Reaction of [V(X)(OR)3] (X=O, Np-tolyl; R=Et, nPr or tBu) with p-tert-butylhexahomotrioxacalix[3]areneH3, LH3, affords the air-stable complexes [{V(X)L}n] (X=O, n=1 (1); X=Np-tolyl, n=2 (2)). Alternatively, 1 is readily available either from interaction of [V(mes)3THF] with LH3, and subsequent oxidation with O2 or upon reaction of LLi3 with [VOCl3]. Reaction of [V(Np-tolyl)(OtBu)3] with 1,3-dimethylether-p-tert-butylcalix[4]areneH2, Cax(OMe)2(OH)2, afforded [{VO(OtBu)}2(mu-O)Cax(OMe)2(O)2].2 MeCN (42 MeCN), in which two vanadium atoms are bound to just one calix[4]arene ligand; the n-propoxide analogue of 4, namely [{VO(OnPr)}2(mu-O)Cax(OMe)2(O)2].1.5 MeCN (51.5 MeCN), has also been isolated from a similar reaction using [V(O)(OnPr)3]. Reaction of [VOCl3], LiOtBu, (Me3Si)2O and Cax(OMe)2(OH)2 gave [{VO(OtBu)Cax(OMe)2(O)2}2Li4O2].8 MeCN (68 MeCN), in which an Li4O4 cube (two of the oxygen atoms are derived from the calixarene ligands) is sandwiched between two Cax(OMe)2(O)2. The reaction between [V(Np-tolyl)(OtBu)3] and Cax(OMe)2(OH)2, afforded [V(Np-tolyl)(OtBu)2Cax(OMe)2(O)(OH)]5 MeCN (75 MeCN), in which two tert-butoxide groups remain bound to the tetrahedral vanadium atom, which itself is bound to the calix[4]arene through only one phenolic oxygen atom. Reaction of p-tert-butylcalix[4]areneH4, Cax(OH)4 and [V(Np-tolyl)(OnPr)3] led to loss of the imido group and formation of the dimeric complex [{VCax(O)4(NCMe)}2].6 MeCN (86 MeCN). Monomeric vanadyl oxo- and imidocalix[4]arene complexes [V(X)Cax(O)3(OMe)(NCMe)] (X=O (11), Np-tolyl (12)) were obtained by the reaction of the methylether-p-tert-butylcalix[4]areneH3, Cax(OMe)(OH)3, and [V(X)(OR)3] (R=Et or nPr). Vanadyl calix[4]arene fragments can be linked by the reaction of 2,6-bis(bromomethyl)pyridine with Cax(OH)4 and subsequent treatment with [VOCl3] to afford the complex [{VOCax(O)4}2(mu-2,6-(CH2)2C5H3N)].4 MeCN (134 MeCN). The compounds 1-13 have been structurally characterised by single-crystal X-ray diffraction. Upon activation with methylaluminoxane, these complexes displayed poor activities, however, the use of dimethylaluminium chloride and the reactivator ethyltrichloroacetate generates highly active, thermally stable catalysts for the conversion of ethylene to, at 25 degrees C, ultra-high-molecular-weight (>5, 500,000), linear polyethylene, whilst at higher temperature (80 degrees C), the molecular weight of the polyethylene drops to about 450,000. Using 1 and 2 at 25 degrees C for ethylene/propylene co-polymerisation (50:50 feed) leads to ultra-high-molecular-weight (>2,900,000) polymer with about 14.5 mol% propylene incorporation. The catalytic systems employing the methyleneoxa-bridged complexes 1 and 2 are an order of magnitude more active than the bimetallic complexes 5 and 13, which, in turn, are an order of magnitude more active than pro-catalysts 8, 11 and 12. These differences in activity are discussed in terms of the structures of each class of complex.

Magnesium and zinc complexes of the monoanionic ligands N,N'-bis(2,6-di-isopropylphenyl)triazenide, L1, N,N'-bis(2,6-di-isopropylphenyl)acetamidinate, L2, and N,N'-bis(2,6-di-isopropylphenyl)tert-butylamidinate, L3, have been synthesized, but only L3 possesses sufficient steric bulk to prevent bis-chelation. Hence, the reaction of L1H with excess ZnEt2 leads to the isolation of (L1)2Zn, 1; L1H also reacts with Bu2Mg in Et2O to afford (L1)2Mg(Et2O), 2. Similar reactivity is observed for L2H, leading to the formation of (L2)2Zn, 3, and (L2)2Mg, 4. The reaction of L2H with ZnR2 may also afford the tetranuclear aggregates {(L2)Zn2R2}2O, 5 (R=Me) and 6 (R=Et). By contrast, the tert-butylamidinate ligand was found to exclusively promote mono-chelation, allowing (L3)ZnCl(THF), 7, [(L3)Zn(micro-Cl)]2, 8, (L3)ZnN(SiMe3)2, 9, (L3)MgiPr(Et2O), 10, and (L3)MgiPr(THF), 11, to be isolated. X-ray crystallographic analyses of 1, 2, 3, 4, 5, 6, 8, and 10 indicate that the capacity of L3 to resist bis-chelation is due to greater occupation of the metal coordination sphere by the N-aryl substituents.

The tin(ii) coordination chemistry of two monoanionic N,N'-bis(2,6-diisopropylphenyl)alkylamidinate ligands is described. Complexation studies with the acetamidinate, [MeC(NAr)(2)](-), (Ar = 2,6-(i)Pr(2)C(6)H(3)) are complicated by the side formation of the bis(amidinate) tin(ii) compound, [MeC(NAr)(2)](2)Sn. By contrast, the bulkier tert-butylamidinate, [(t)BuC(NAr)(2)](-), allows tin(ii) mono-halide, -alkoxide and -amide complexes to be isolated cleanly in high yields. Thus, the reaction of [(t)BuC(NAr)(2)]H with (n)BuLi and subsequent treatment with SnCl(2) generates [(t)BuC(NAr)(2)]SnCl, in ca. 70% yield. Reactions of with LiO(i)Pr, LiNMe(2) and LiNTMS(2) afford [(t)BuC(NAr)(2)]Sn(O(i)Pr), [(t)BuC(NAr)(2)]Sn(NMe(2)), and [(t)BuC(NAr)(2)]Sn(NTMS(2)), respectively. The molecular structures of complexes are reported. Complexes, and have been investigated as initiators for the ring-opening polymerisation of rac-lactide: and display characteristics of well-controlled polymerisation initiators, but high molecular weight polymer is observed with due to inefficient initiation, a consequence of the steric bulk of the NTMS(2) unit. Polymerisations with and are faster than for the corresponding beta-diketiminate tin(ii) complexes, consistent with the more open nature of the tin(ii) coordination sphere.

Transforming a carbon-hydrogen bond of an organic compound into a more useful, more reactive carbon-metal bond (so-called deprotonative metalation), which, in turn, can be treated with an electrophile to create a new carbon-carbon or carbon-heteroatom bond, is one of the most fundamental synthetic approaches that chemists employ to construct compounds. [1,2] Many of these reactions involve a special type of deprotonative metalation, in which an activating functional group is positioned adjacent to the hydrogen atom (strictly a proton) that is to be replaced by the metal cation.

Vanadyl complexes of C or N-capped tripodal ligands, possessing distorted tetrahedral geometry at vanadium, serve as extremely active, thermally robust pro-catalysts for ethylene homo- and ethylene/propylene copolymerisation, whereas pseudo-octahedral pro-catalysts produce far lower activities.

No abstract

Lithium dialkyl tetramethylpiperidino zincates of the general formula "[LiR 2 Zn(tmp)]" (tmp = 2,2,6,6-tetramethylpiperidine) represent an important subfamily of organozincate reagent. Established only in 1999 through the pioneering work on "[LitBu 2 Zn(tmp)]" by Kondo et al., [1] "tmp zincates" have found application as highly chemo-and/or regioselective bases for the metalation of alkyl benzoates and related aza aromatic compounds, bromopyridines, and various halobenzenes. [2,3] Recent reports [4] have highlighted the poverty of structural information available on lithium zincates in general. Tmp zincates are no exception in this regard, with a 13 C NMR spectroscopic study of "[LitBu 2 Zn(tmp)]" in solution [1] providing the only morsel of structural evidence