Biimidazole and bis(amide)bipyridine molybdenum carbonyl complexes as anions receptors.

Compounds [Mo(CO)4(N-N)] (N-N = 4,4'-bis((4-methylphenyl)carbamoyl)-2,2'-bipyridine, bipy', 1; or 2,2'-biimidazole, H2biim, 2), [MoCl(eta3-methallyl)(CO)2(N-N)] (N-N = bipy', 3; H2biim, 4), and [Mo(eta3-methallyl)(CNtBu)(CO2)(N-N)]BAr'4 (Ar' = 3,5-bis(trifluoromethyl)phenyl; N-N= bipy', 5; H2biim, 6) were synthesized and characterized, and their behavior toward anions was investigated in solution (IR and 1H NMR) and in solid state (X-ray diffraction).

Pyridyl 'ring-flipping' in the dimers [Me2E(2-py)]2 (E=B, Al, Ga; 2-py=2-pyridyl).

The boron and aluminium dimers [Me2E(micro-py)]2 [E=B (1); Al (2)] are formed as mixtures of two isomers in which the group 13 centres are coordinated by the bridging 2-py ligands in a cis or trans manner, however, in contrast to previous studies, we find that simply heating the mixtures of these isomers of and gives the more thermodynamically stable (synthetically useful) trans isomers exclusively (the trans isomer being the only product in the case of the gallium analogue ).

Structural, solid-state NMR and theoretical studies of the inverse-coordination of lithium chloride using group 13 phosphide hosts.

The reaction of MeAlCl2 with 'PhPLi2' in THF gives [{MeAl(PPh)3Li(4).3 THF}4(mu4-Cl)]-Li+ (1). The GaIII and InIII analogues, [{MeE(PPh)3Li(4).

Targeting large phosp(III)azane macrocyles [{P(mu-NR)}(2)(LL)](n) (n> or = 2).

The condensation reactions of the dimer [ClP(micro-NR)](2) with organic diacids [LL(H)(2)], possessing linear orientations of their organic groups, result in the formation of phospha(III)zane macrocyles of the type [{P(mu-NR)}(2)(LL)](n) of various sizes. The series of macrocycles [{P(mu-N(t)Bu)}(2){1,5-(NH)(2)C(10)H(6)}](3), [{P(mu-NCy)}(2)(1,5-O(2)C(10)H(6))](n) [n = 3; n = 4], [{P(mu-N(t)Bu)}(2){1,4-(NH)(2)C(6)H(4)}](4), [{P(mu-N(t)Bu)}(2)(1,4-O(2)C(6)H(4))], [{P(mu-NCy)}(2)(1,4-O(2)C(6)H(4))](3) and [{P(mu-N(t)Bu)}(2){(NH)C(6)H(4)OC(6)H(4)(NH)}](2) can be related to classical organic frameworks, like calixarenes.

Ruthenium biimidazole complexes as anion receptors.

The behavior of the compound [RuCl(cym)(H2biim)][BAr'4] (cym = eta6-para-isopropylmethylbenzene, Ar' = 3,5-bis(trifluoromethyl)phenyl), synthesized from [[RuCl(cym)]2(mu-Cl)2], H2biim and NaBAr'4, has been studied as a receptor of anions both in solution and in the solid state.

The folded, tetrameric phosph(III)azane macrocycle [(P(mu-NtBu))2(1,4-(NH)2C6H4)]4.

The tetrameric macrocycle [(P(mu-NtBu))2(1,4-(NH)2C6H4)]4, obtained from the reaction of the phosphazane dimer [ClP(mu-NtBu)]2 with p-phenylenediamine, has an unusual folded conformation in the solid state and contains a roughly tetrahedral arrangement of endo N-H groups for the potential coordination of anions.

Synthesis and structure of the calixarene-like phosph(III)azane macrocycle [{P(mu-N(t)Bu)}2{1,5-(NH)2C10H6}]3.

The reaction of [ClP(mu-NtBu)]2 with 1,5-diamino-naphthalene [1,5-(NH2)2C10H6] in Et3N-thf gives the trimeric macrocycle [{P(mu-NtBu)}2{1,5-(NH)2C10H6}]3(1); the X-ray structure of the toluene solvate 1.3toluene reveals a cone-shaped (calixarene-like) arrangement in which toluene guest molecules are trapped within the cavity.

Triphosph(III)azanes to diphosph(III)azanes; a cracking transformation.

The reversible interconversion between trimeric [ClPNEt]3 and dimeric [ClPNEt]2 reported here is the first observation of such a thermally induced rearrangement between two cyclophosphazane oligomers; the structure of 1.cis is reported along with NMR studies of its conversion into 2.

Selection of the cis and trans phosph(III)azane macrocycles [{P(mu-NtBu)}2(1-Y-2-NH-C6H4)]2(Y=O, S).

The 1 : 1 reactions of [ClP(mu-NtBu)]2 with the difunctional aromatic amines 1,2-1-YH-2-NH2-C6H4 in the presence of Et3N give the dimeric phosph(III)azane macrocycles [{P(mu-NtBu)2(1-Y-2-HN-C6H4)]2, predominantly as the cis isomer in the case of Y=O (1.cis) and as the trans isomer for Y=S (2.trans).

Highly selective epoxidation of styrene using a transition metal-aluminium(III) complex containing the [MeAl(2-py)3]- anion (2-py = 2-pyridyl).

The reactions of [MeAl(2-py)3Li.thf] (1) with FeCl2 or Cp2Mn in toluene-thf give simple access to the Group 13-transition metal heterometallic complexes [{MeAl(2-py)3}2M][M = Fe (2), Mn (3)]; complex has been shown to be a highly selective styrene epoxidation catalyst in air.

Selection of a pentameric host in the host-guest complexes [[[[P(mu-NtBu)]2(mu-NH)]5].I]-[Li(thf)4]+ and [[[P(mu-NtBu)]2(mu-NH)]5].HBr.THF.

The structures of the host-guest complexes [[[[P(mu-NtBu)]2(mu-NH)]5]I]-.[Li(thf)4]+ [2.I[Li(thf)4]] and [[[P(mu-NtBu)]2(mu-NH)]5].

Syntheses, structures and magnetic properties of Mn(II) dimers [CpMn(micro-X)]2(Cp = C5H5; X = RNH, R1R2N, C[triple bond]CR).

Manganocene, Cp(2)Mn, has been employed as a precursor in the synthesis of a range of Mn(II) dimers of the type [CpMn(micro-X)](2)[X = 8-NHC(9)H(6)N (1), N(Ph)(C(5)H(4)N)(2), N(4-EtC(6)H(4))(C(5)H(4)N)(3) and C[triple bond]CPh (4)] as well as the bis-adduct [Cp(2)Mn[HN=C(NMe(2))(2)](2)](5). The solid-state structures of 1-5 are reported. Variable-temperature magnetic measurements have been used to assess the extent of Mn(micro-X)Mn communication within the dimers of 1-4 as a function of the bridging ligands (X).

The formation of dimeric phosph(III)azane macrocycles [[P(mu-NtBu)]2.LL]2 [LL = organic spacer].

The dimeric macrocycles [[P(mu-NtBu)]2.LL]2 [LL = OCH2C(Me)2CH2O (1), 2,6-(NH)2C5H3N (2), 1,2-(NH)2C6H4(3)] have been obtained by the reactions of the appropriate diols and diamines (LLH2) with the dimeric phosph(III)azane [ClP(mu-NtBu)]2. Under different conditions the reaction of 1,2-(NH2)2C6H4 with [ClP(mu-NtBu)]2 gives the monomer [[P(mu-NtBu)]2.

Selective formation of the [PhP(H)-PPh]- anion in the reaction of PhPHLi with MeAlCl(2); synthesis and structure of the unusual tetramer [(PhP(H)-PPh)Li.thf]4.

The reaction of PhPHLi with MeAlCl(2)(3:1 equivalents) gives the tetramer [(PhP(H)-PPh)Li.thf]4, and provides the first direct evidence of a link between the reactivity patterns observed for Group 14 and 15 phosphanenides and those of Group 13.

Steric control in the oligomerisation of phosphazane dimers; towards new phosphorus-nitrogen macrocycles.

The reaction of [ClP(mu-NtBu)]2 (1) with H2O (1 : 2 equivalents) in the presence of excess Et3N gives the new chain compound [(mu-O)[P(mu-NtBu)2P(H)=O]2] (3), consisting of two P2N2 rings linked by a mu-O atom and terminating in P(V)(H)=O groups. A similar chain species is obtained from the reaction of the lithiate of [(tBuNH)P(mu-NtBu)2P(H)=O] (5) with [ClP(mu-NtBu)2P(NHtBu)] (2), the product being [(mu-O)[P(mu-NtBu)2P(NHtBu)]2] (6). Compounds 3 and 6 are the first examples of O-bridged chain phosphazanes and potential precursors to new phosphorus-nitrogen macrocycles.

A one-pot synthesis to [(Me3Si)3SiSb]4; a potential precursor for Sb42-.

The reaction of (Me(3)Si)(3)SiK[middle dot]18-crown-6 with SbCl(3)(3 : 1 equiv.) provides a simple route to the title complex [(Me(3)Si)(3)SiSb](4). The potassium base initially acts as a nucleophile and then as a coupling agent, forming Sb-Sb bonds.

thermodynamic/kinetic control in the isomerization of the [[tBuNP(mu-NtBu)]2]2- ion.

The unique structure of [(tBuN)(2)PK]( infinity ) (2) (containing [(tBuN)(2)P](-) monoanions) is in stark contrast to the previously reported Li(+) analogue [[[tBuNP(mu-NtBu)](2)](2)]Li(4) (1) (containing the dimeric [[tBuNP(mu-NtBu)](2)](2-) ion). DFT and (31)P NMR spectroscopic studies reveal that the formation of the monoanion arrangements are most thermodyamically favored for Li, Na, and K, 1 being the product of kinetic control and 2 being the product of thermodynamic control.

Exo-metal coordination by a tricyclic [(P(mu-N-2-NC5H4))2(mu-O)]2 dimer in [(P(mu-N-2-NC5H4))2(mu-O)]2(CuCl x (C5H5N)2)4 (2-NC5H4 = 2-pyridyl, C5H5N = pyridine).

The in situ reaction of the phosphazane dimer [CIP(mu-N-2-NC5H4)]2 (2) with CuCl in the presence of CsH5N/H2O gives the title complex [(P(mu-N-2-NC5H4))2(mu-O)]2(CuCl x (C5H5N)2)4 (1), containing a tricyclic [(P(mu-N-2-NC5H4))2(mu-O)]2 ligand which is isoelectronic with species of the type [(P(mu-NR))2NR]2.