Two complexes of CuBr(2) with 5-tert-butylpyrazole.

trans-Dibromobis(5-tert-butylpyrazole-N(2))copper(II), trans-[CuBr(2)(Hpz(tBu))(2)] (Hpz(tBu) is 5-tert-butylpyrazole, C(7)H(12)N(2)), exhibits a distorted square-planar geometry with a significant tetrahedral twist, while trans-dibromotetrakis(5-tert-butylpyrazole-N(2))copper(II), trans-[CuBr(2)(Hpz(tBu))(4)], adopts a distorted octahedral geometry across a crystallographic inversion centre. Both compounds exhibit intramolecular N--H...Br hydrogen-bonding interactions.

Synthesis, structures, and reactivity of weakly coordinating anions with delocalized borate structure: the assessment of anion effects in metallocene polymerization catalysts.

The formation of adducts of tris(pentafluorophenyl)borane with strongly coordinating anions such as CN(-) and [M(CN)(4)](2)(-) (M = Ni, Pd) is a synthetically facile route to the bulky, very weakly coordinating anions [CN[B(C(6)F(5))(3)](2)](-) and [M[CNB(C(6)F(5))(3)](4)](2-) which are isolated as stable NHMe(2)Ph(+) and CPh(3)(+) salts. The crystal structures of [CPh(3)][CN[B(C(6)F(5))(3)](2)] (1), [CPh(3)][ClB(C(6)F(5))(3)] (2), [NHMe(2)Ph](2)[Ni[CNB(C(6)F(5))(3)](4)].2Me(2)CO (4b.2Me(2)CO), [CPh(3)](2)[Ni[CNB(C(6)F(5))(3)](4)].2CH(2)Cl(2) (4c.2CH(2)Cl(2)), and [CPh(3)](2)[Pd[CNB(C(6)F(5))(3)](4)].2CH(2)Cl(2) (5c.2CH(2)Cl(2)) are reported. The CN stretching frequencies in 4 and 5 are shifted by approximately 110 cm(-1) to higher wavenumbers compared to the parent tetracyano complexes in aqueous solution, although the M-C and C-N distances show no significant change on B(C(6)F(5))(3) coordination. Zirconocene dimethyl complexes L(2)ZrMe(2) [L(2) = Cp(2), SBI = rac-Me(2)Si(Ind)(2)] react with 1, 4c or 5c in benzene solution at 20 degrees C to give the salts of binuclear methyl-bridged cations, [(L(2)ZrMe)(2)(mu-Me)][CN[B(C(6)F(5))(3)](2)] and [(L(2)ZrMe)(2)(mu-Me)](2)[M[CNB(C(6)F(5))(3)](4)]. The reactivity of these species in solution was studied in comparison with the known [[(SBI)ZrMe](2)(mu-Me)][B(C(6)F(5))(4)]. While the latter reacts with excess [CPh(3)][B(C(6)F(5))(4)] in benzene to give the mononuclear ion pair [(SBI)ZrMe(+).B(C(6)F(5))(4)(-)] in a pseudo-first-order reaction, k = 3 x 10(-4) s(-1), [(L(2)ZrMe)(2)(mu-Me)][CN[B(C(6)F(5))(3)](2)] reacts to give a mixture of L(2)ZrMe(mu-Me)B(C(6)F(5))(3) and L(2)ZrMe(mu-NC)B(C(6)F(5))(3). Recrystallization of [Cp' '(2)Zr(mu-Me)(2)AlMe(2)][CN[B(C(6)F(5))(3)](2)] affords Cp' '(2)ZrMe(mu-NC)B(C(6)F(5))(3) 6, the X-ray structure of which is reported. The stability of [(L(2)ZrMe)(2)(mu-Me)](+)X(-) decreases in the order X = [B(C(6)F(5))(4)] > [M[CNB(C(6)F(5))(3)](4)] > [CN[B(C(6)F(5))(3)](2)] and increases strongly with the steric bulk of L(2) = Cp(2) << SBI. Activation of (SBI)ZrMe(2) by 1 in the presence of AlBu(i)(3) gives extremely active ethene polymerization catalysts. Polymerization studies at 1-7 bar monomer pressure suggest that these, and by implication most other highly active ethene polymerization catalysts, are strongly mass-transport limited. By contrast, monitoring propene polymerization activities with the systems (SBI)ZrMe(2)/1/AlBu(i)(3) and CGCTiMe(2)/1/AlBu(i)(3) at 20 degrees C as a function of catalyst concentration demonstrates that in these cases mass-transport limitation is absent up to [metal] approximately 2 x 10(-5) mol L(-1). Propene polymerization activities decrease in the order [CN[B(C(6)F(5))(3)](2)](-) > [B(C(6)F(5))(4)](-) > [M[CNB(C(6)F(5))(3)](4)](2-) >> [MeB(C(6)F(5))(3)](-), with differences in activation barriers relative to [CN[B(C(6)F(5))(3)](2)](-) of DeltaDeltaG = 1.1 (B(C(6)F(5))(4)(-)), 4.1 (Ni[CNB(C(6)F(5))(3)](4)(2-)) and 10.7-12.8 kJ mol(-)(1) (MeB(C(6)F(5))(3)(-)). The data suggest that even in the case of very bulky anions with delocalized negative charge the displacement of the anion by the monomer must be involved in the rate-limiting step.

Bis[tris(3-cyclohexylpyrazol-1-yl)-hydridoborato]copper(II) dichloromethane disolvate.

The title compound, [Cu(C27H40BN6)2]*2CH2Cl2, contains a four-coordinate Cu(II) ion lying on a crystallographic inversion centre, giving rise to a near-regular square-planar stereochemistry. There is an axial contact of 2.71 A between the Cu ion and ligand B-H group, although this is unlikely to correspond to a significant 'agostic' interaction.

Ten-vertex rhodadithiaborane chemistry:.

Neutral 8-(5-iodo-n-pentyl)-3-(eta(5)-pentamethylcyclopentadienyl)-arachno-3-rhoda-7,8-dithiaundecaborane, [Rh(C(5)H(19)B(8)IS(2))(C(10)H(15))], obtained from the [arachno-7,8-S(2)B(9)H(10)](-) anion by treatment with I(CH(2))(5)I followed by [Rh(C(5)Me(5))Cl(2)](2) and N,N,N',N'-tetramethyl-1,8-diaminonaphthalene, has the 11-vertex cluster geometry of [arachno-7,8-S(2)B(9)H(10)](-), but with an [Rh(C(5)Me(5))] unit in the 3-position instead of a [BH] unit, and with a -(CH(2))(5)I chain attached exo to an S atom.

1-(Dibromomethyl)-4-methoxy-2-methylbenzene.

The title compound, C(9)H(10)Br(2)O, is a major product of the radical bromination of 4-methoxy-1,2-dimethylbenzene. Each Br atom is involved in a close contact with the O atom of a neighbouring molecule, forming a geometry that is suggestive of weak intermolecular O--> Br charge-transfer interactions.

N-monofunctionalized 1,4,7-triazacyclononane macrocycles as building blocks in inorganic crystal engineering.

The syntheses of N-(3-prop-1-ene)-1,4,7-triazacyclononane molybdenum tricarbonyl (2), N-(4-but-1-ene)-1,4,7-triazacyclononane molybdenum tricarbonyl (3), N-(3-prop-1-ene)-1,4,7-triazacyclononane molybdenum trioxide (5), N-(4-but-1-ene)-1,4,7-triazacyclononane molybdenum trioxide (6), N-(hydroxyethyl)-1,4,7-triazacyclononane molybdenum trioxide (7), and N-(2-methylpyridyl)-1,4,7-triazacyclononane molybdenum trioxide (8) have been achieved. The objective of this work is to systematically vary the functionality of the pendant group in order to create different crystal packing in the solid state. This is evidenced in comparing the structures of 1,4,7-triazacyclononane molybdenum trioxide (4) and 5-8, which were determined using X-ray crystallography. The synthesis and characterization of the new ligand N-(2-methylpyridyl)-1,4,7-triazacyclononane (L5) is reported.

A novel route to substituted 4-methylene-4,5-dihydroisoxazoles mediated by hafnium(IV) chloride.

Heating alkyl vinyl ketones and N-tert-butylarylmethylideneamine N-oxides in the presence of HfCl4 results in the formation of 4-methylene-4,5-dihydroisoxazoles in good yield.

Monocarbaborane chemistry. Preparation and characterisation of [4-CB8H9]-, the 'missing' closo-carbaborane anion.

Thermolysis in the solid state of Cs+[arachno-CB9H14]-, or of Cs+[nido-CB9H12]-, or the oxidation of nido-1-CB8H12 with I2 in THF at -78 degrees C in the presence of NEt3, gives the first nine-vertex closo monocarbaborane, the stable [closo-4-CB8H9]- anion, in yields of 56, 61 and 75%, respectively.

Triple linking of the decaboranyl cluster. Structure of [(SMe2)2B10H10(B10H13)2] as determined by synchrotron X-ray diffraction analysis.

In an attempt to find generic routes to multiple inter-cluster sigma-linking, mild thermolysis of [6,9-(SMe2)2-arachno-B10H12] 1 in inert hydrocarbon solution gives the tridecaboranyl species [6,9-(SMe2)2-arachno-B10H(10)-1,5-(6'-nido-B10H13)2] 3 (23%).

Monocarbaborane anion chemistry. The elusive C-arylated [PhCB11H11]-, [PhCB9H9]- and [PhCB8H8]- anions.

B10H14 and PhCHO yield [6-Ph-nido-6-CB9H11]- (94%), from which the nine-vertex C-phenyl monocarbaborane anion [4-Ph-closo-4-CB8H8]- (68%) can be obtained by heating at 200 degrees C, and from which the twelve- and ten-vertex analogues [1-Ph-closo-1-CB11H11]- (50%) and [4-Ph-closo-4-CB9H9]- (25%) can be obtained by heating at 210 degrees C with BH3(NEt3).

Bis2,6-bis

The title compound, [Zn(C(29)H(29)N(5))(2)](ClO(4))(2).2CH(3)NO(2), contains a Zn(II) ion showing only small deviations from local D(2d) symmetry. The lower rhombicity exhibited by this complex compared with that of its Cu(II) congener suggests that the highly rhombic stereochemistry exhibited by the latter is largely imposed by the stereoelectronic preferences of the Cu(II) ion.

[1,1,2,2-]

The title compound, 1,1,2,2-tetracarbonyl-1,2-&mgr;-carbonyl-4, 11-dimethylsulfido-closo-1,2-dicobaltadodecaborane, [Co(2)(C(4)H(20)B(10)S(2))(CO)(5)], has a closo 12-vertex 1, 2-Co(2)B(10)H(8) structure with SMe(2) ligands at the exo-4- and 11-positions. The cluster displays close structural similarities to the SEt(2) analogue.

4'-Vinyl-2,2':6',2"-terpyridine

The title compound, C(17)H(13)N(3), is a versatile precursor for polymeric terpyridine derivatives and their metal complexes. The molecule has transoid and near-coplanar pyridine rings. However, the vinyl group is forced out of the plane of the terpyridyl moiety by a close H.H contact.