Formation of two diverse classes of poly(amino-alkoxide) chelates and their mononuclear and polynuclear lanthanide(III) complexes.

Factors that influence aggregation of lanthanide(III) (Ln(III)) ions to form polynuclear complexes were studied utilizing 1-aziridineethanol as a versatile source of macrocyclic and acyclic chelates. The facile ring-opening cyclo-oligomerization of 1-aziridineethanol leads to the formation of a series of polyaza cyclic oligomers (series A). In the presence of ethylenediamine, a competing N-alkylation reaction occurs to produce a new class of acyclic ligands (series B).

Transition metal-catalyzed formation of boron-nitrogen bonds: catalytic dehydrocoupling of amine-borane adducts to form aminoboranes and borazines.

A mild, catalytic dehydrocoupling route to aminoboranes and borazine derivatives from either primary or secondary amine-borane adducts has been developed using late transition metal complexes as precatalysts. The adduct Me(2)NH.BH(3) thermally eliminates hydrogen at 130 degrees C in the condensed phase to afford [Me(2)N-BH(2)](2) (1).

Adducts of hexamethylenetetramine with ferrocenecarboxylic acid and ferrocene-1,1'-dicarboxylic acid: multiple disorder in space groups Fmm2 and Cmcm.

Hexamethylenetetramine, C(6)H(12)N(4), and ferrocenecarboxylic acid, C(11)H(10)FeO(2), form a 1:2 adduct, (I), which is a salt, viz. hexamethylenetetraminium(2+) bis(ferrocenecarboxylate), (C(6)H(14)N(4))[Fe(C(5)H(5))(C(6)H(4)O(2))](2). The dication in (I) is disordered with two orientations at a site of mm2 symmetry in space group Fmm2, while the anion lies across a mirror plane with its unsubstituted cyclopentadienyl ring disordered over two sets of sites.

meso-5,5,7,12,12,14-Hexamethyl-4,11-diaza-1,8-diazoniacyclotetradecane (S)-malate(2-) methanol disolvate: a chain of rings generated by two pairs of N-H.O hydrogen bonds.

The title compound is a methanol-solvated salt, C(16)H(38)N(4)(2+).C(4)H(4)O(5)(2-).2CH(3)OH, in which the ionic components are linked into chains by two pairs of N-H.

meso-5,5,7,12,12,14-hexamethyl-1,4-diaza-8,11-diazoniacyclotetradecane bis(2-naphthoate) ethanol disolvate: centrosymmetric five-component aggregates linked into sheets by C-H...pi(arene) hydrogen bonding.

The title compound is an ethanol-solvated salt, C(16)H(38)N(4)(2+) x -2C(11)H(7)O(2)(-) x -2C(2)H(6)O, in which the cation lies across a centre of inversion in P2(1)/c. The ions are linked by N-H..

The 1:1 adduct of triphenylsilanol and 4,4'-bipyridyl, and three pairwise-concomitant triclinic polymorphs of the 4:1 adduct having Z' = 0.5, 1 and 4.

Crystallization from methanol solution of mixtures of triphenylsilanol and 4,4'-bipyridyl has given a 1:1 adduct (I), Ph(3)SiOH.C(10)H(8)N(2), and three polymorphic 4:1 adducts (II)-(IV), (Ph(3)SiOH)(4).C(10)H(8)N(2).

Phosphonopropionic acid as a building block in supramolecular chemistry: salts with organic diamines.

The structures of seven salts formed by phosphonopropionic acid with organic diamines are reported; in these salts, the hydrogen-bonded substructures formed by the anions can be zero-, one- or two-dimensional, while the overall hydrogen-bonded supramolecular structures are three-dimensional. The 1:1 adduct, compound (1), formed between 1,2-bis(4'-pyridyl)ethene and phosphonopropionic acid is a salt, [[(C(12)H(10)N(2))H(2)](2+)].[(C(12)H(10)N(2))].

(1R,3S)-Camphoric acid as a building block in supramolecular chemistry: adducts with organic polyamines.

(1R,3S)-Camphoric acid [(1R,3S)-1,2,2,-trimethylcyclopentane-1,3-dicarboxylic acid, C(10)H(16)O(4)] forms adducts with a range of amines in which the acid component may be the neutral molecule, the mono-anion (C(10)H(15)O(4))(-) or the di-anion (C(10)H(14)O(4))(2-). The structures generated by the hard hydrogen bonds take the form of chains in the 1:1 adducts (II) and (III) formed with 4,4'-bipyridyl and 1,2-bis(4-pyridyl)ethane. There are single sheets in the hydrated 1:1 adduct (IV) formed with 1,4-diazabicyclo[2.

Salts of maleic and fumaric acids with organic polyamines: comparison of isomeric acids as building blocks in supramolecular chemistry.

Maleic acid and fumaric acid both readily form adducts with organic diamines: maleic acid usually forms 2:1 adducts with bases, while fumaric acid usually forms 1:1 adducts, and the supramolecular structures within the two series are not simply related. The 1:2 adducts formed by 1,2-bis(4-pyridyl)ethane and by 4,4'-bipyridyl, respectively, with maleic acid, compounds (1) and (2), are salts [(diamine)H(2)(2+)].[(C(4)H(3)O(4))(-)](2) in which the cations lie across a centre of inversion and a twofold rotation axis, respectively.

Chemistry of phosphine-borane adducts at platinum centers: synthesis and reactivity of PtII complexes with phosphinoborane ligands.

Reaction of [Pt(PEt(3))(3)] with the primary and secondary phosphine-borane adducts PhRPH x BH(3) (R=H, Ph) resulted in oxidative addition of a P-H bond at the Pt(0) center to afford the complexes trans-[PtH(PPhR x BH(3))(PEt(3))(2)] (1: R=H; 2: R=Ph). The products 1 and 2 were characterized by (1)H, (11)B, (13)C, (31)P, and (195)Pt NMR spectroscopy, and the molecular structures were verified by X-ray crystallography. In both cases, a trans arrangement of the hydride ligand with respect to the phosphidoborane ligand was observed.

Mechanism of the hydrogenation of ketones catalyzed by trans-dihydrido(diamine)ruthenium II complexes.

The complexes trans-RuH(Cl)(tmen)(R-binap) (1) and (OC-6-43)-RuH(Cl)(tmen)(PPh(3))(2) (2) are prepared by the reaction of the diamine NH(2)CMe(2)CMe(2)NH(2) (tmen) with RuH(Cl)(PPh(3))(R-binap) and RuH(Cl)(PPh(3))(3), respectively. Reaction of KHB(sec)Bu(3) with 1 yields trans-Ru(H)(2)(R-binap)(tmen) (5) while reaction of KHB(sec)Bu(3) or KO(t)Bu with 2 under Ar yields the new hydridoamido complex RuH(PPh(3))(2)(NH(2)CMe(2)CMe(2)NH) (4). Complex 4 has a distorted trigonal bipyramidal geometry with the amido nitrogen in the equatorial plane.

Triple C-H activation of 1,5-bis(di-tert-butylphosphino)-2-(S)-dimethylaminopentane on ruthenium gives a chiral carbene complex.

This communication reports the preparation of a novel trans-chelating diphosphine, 1,5-bis(di-tert-butylphosphino)-2-(S)-dimethylaminopentane, that undergoes triple C-H activation in reaction with [RuCl2(p-cymene)]2 to give a chiral square-pyramidal 16-electron carbene complex of ruthenium.

Metallochain cluster complexes and metallomacrocyclic triangles based on coordination bonds between palladium or platinum and diphosphinoacetylene ligands.

To explore the potential of the coordination chemistry of Pd and Pt halides with phosphinoacetylene ligands for the generation of novel, highly metallated organometallic coordination polymers, investigations on model compounds [MX2(PPh2 C identical to CPh)2] that exhibit trans-configured Pd centers and cis-configured Pt centers have been performed. The molecular structure of the trans-Pd complexes 2 (M = Pd, X = Br) and 5 (M = Pd, X = I) appeared suitable for the generation of linear materials, whereas the cis-Pt complex 6 (M = Pt, X = I) suggested the prospective formation of ring systems. The presence of acetylene moieties allowed for further increase of metal concentration by cluster formation with [Co2(CO)8].

Ferrocene-1,1'-dicarboxylic acid as a building block in supramolecular chemistry: supramolecular structures in one, two and three dimensions.

The supramolecular structures have been determined for nine adducts formed between organic diamines and ferrocene-1,1'-dicarboxylic acid. In the salt-like 1:1 adduct (1) formed with methylamine, the supramolecular structure is one-dimensional, whereas in the 1:1 adducts formed with 1,4-diazabicyclo[2.2.

Bis(trichlorophosphine)iminium salts, [Cl3P=N=PCl3]+, with transition metal halide counter-ions.

The structures of four bis(trichlorophosphine)iminium [[Cl(3)P=N=PCl(3)](+); systematic name: trichloro[(trichlorophosphoranylidene)iminio]phosphorus(V)] salts, namely bis(trichlorophosphine)iminium hexachloroniobate, (Cl(6)NP(2))[NbCl(6)], (I), bis(trichlorophosphine)iminium hexachlorotantalate, (Cl(6)NP(2))[TaCl(6)], (II), bis(trichlorophosphine)iminium tri-micro-chloro-bis[trichlorotitanium(IV)], (Cl(6)NP(2))[Ti(2)Cl(9)], (III), and bis[bis(trichlorophosphine)iminium] di-micro-chloro-bis[tetrachlorozirconium(IV)], (Cl(6)NP(2))(2)[Zr(2)Cl(10)], (IV), have been determined. The P=N distances in the discrete [Cl(3)P=N=PCl(3)](+) moieties in structures (I), (II) and (IV) range from 1.5460 (14) to 1.

Nucleophilically assisted and cationic ring-opening polymerization of tin-bridged [1]ferrocenophanes.

To obtain mechanistic insight, detailed studies of the intriguing "spontaneous" ambient temperature ring-opening polymerization (ROP) of tin-bridged [1]ferrocenophanes Fe(eta-C(5)H(4))(2)SnR(2) 3a (R = t-Bu) and 3b (R = Mes) in solution have been performed. The investigations explored the influence of non-nucleophilic additives such as radicals and radical traps, neutral and anionic nucleophiles, Lewis acids, protic species, and other cationic electrophiles. Significantly, two novel methodologies and mechanisms for the ROP of strained [1]ferrocenophanes are proposed based on this study.

Self-assembled hydrogen-bonded bilayers in 1,4-diazabicyclo[2.2.2]octane-N-(phosphonomethyl)iminodiacetic acid-water (1/1/1.5).

The title compound is a hydrated salt, 1,4-diazoniabicyclo[2.2.2]octane-N-[(hydroxyphosphinato)methyl]iminiodiacetate-water (1/1/1.

Reversible skeletal substitution reactions involving group 13 heterophosphazenes.

The cyclic boratophosphazene, N(PCl2NMe)2BCl2 1, reacts with two equivalents of AlMe3 to give the aluminatophosphazene heterocycle, N(PCl2NMe)2AlClMe 4. The unprecedented reverse skeletal substitution (Al for B) was accomplished by treating 4 with Ag[BF4] to form the fluorinated boratophosphazene N(PCl2NMe)2BF2 5.

N,N'-Dithiobisphthalimide-1,4-dioxan (1/0.6): a C2/c solvate with disordered solvent molecules localized in channels.

N,N'-Dithiobisphthalimide crystallizes from 1,4-dioxan solution as a solvate, 3C(16)H(8)N(2)O(4)S(2) x 1.8C(4)H(8)O(2), having space group C2/c. Four of the 12 C(16)H(8)N(2)O(4)S(2) molecules in the unit cell lie on twofold rotation axes, while the other eight lie in general positions.

Chiral versus racemic building blocks in supramolecular chemistry: malate salts of organic diamines.

(S)-Malic acid forms a salt with N,N'-dimethylpiperazine, [MeN(CH(2)CH(2))(2)NMe]H(2)(2+) x 2C(4)H(5)O(5)(-) (1) (triclinic, P1, Z' = 1), in which the cations link pairs of hydrogen-bonded anion chains to form a molecular ladder. With 4,4'-bipyridyl, (S)-malic acid forms a 1:1 adduct which crystallizes from methanol to yield two polymorphs, (2) (triclinic, P1, Z' = 1) and (3) (monoclinic, C2, Z' = 1), while racemic malic acid with 4,4'-bipyridyl also forms a 1:1 adduct, (4) (monoclinic, P2(1)/c, Z' = 1). In each of (2), (3) and (4) the components are linked by O[bond]H.

Large effects of ion pairing and protonic-hydridic bonding on the stereochemistry and basicity of crown-, azacrown-, and cryptand-222-potassium salts of anionic tetrahydride complexes of iridium(III).

The compounds [K(Q)][IrH(4)(PR(3))(2)] (Q = 18-crown-6, R = Ph, (i)Pr, Cy; Q = aza-18-crown-6, R = (i)Pr; Q = 1,10-diaza-18-crown-6, R = Ph, (i)Pr, Cy; Q = cryptand-222, R = (i)Pr, Cy) were formed in the reactions of IrH(5)(PR(3))(2) with KH and Q. In solution, the stereochemistry of the salts of [IrH(4)(PR(3))(2)](-) is surprisingly sensitive to the countercation: either trans as the potassium cryptand-222 salts (R = Cy, (i)Pr) or exclusively cis (R = Cy, Ph) as the crown- and azacrown-potassium salts or a mixture of cis and trans (R = (i)Pr). There is IR evidence for protonic-hydridic bonding between the NH of the aza salts and the iridium hydride in solution.

Enantiomeric bis(micro-N,N'-hexamethylenedisalicylaldiminato)dicopper(II) complexes.

The title dimeric complex, bis[micro-2,2'-[hexane-1,6-diylbis(nitrilomethylidyne)]diphenolato-1:2kappa(4)O,N:N',O']dicopper(II),[Cu(2)(C(20)H(22)N(2)O(2))(2)], has been investigated by single-crystal X-ray diffraction, by thermogravimetric analysis and differential scanning calorimetry, and also by FT-IR spectroscopy. Different synthetic and crystallization procedures gave crystals which were quite different in appearance, and it was initially thought that these were different polymorphic forms. Subsequent structure determination showed, in fact, serendipitous preparation of crystals in the P4(1) space group by one method and in space group P4(3) by the other.

Carbamoyl-substituted N-heterocyclic carbene complexes of palladium(II): application to Sonogashira cross-coupling reactions.

[reaction: see text]. The first examples of N-carbamoyl-substituted heterocyclic carbene Pd(II) complexes are described. These thermal and hydrolytically stable complexes are readily prepared from carbamoyl imidazolium salts and efficiently promote Sonogashira cross-coupling reactions under mild conditions.