Bis(amido)cyclodiphosph(III)azane complexes of yttrium and the lanthanides.

The first cyclodiphosph(III)azane complexes of the rare-earth elements have been synthesized. Reactions of the lithium salt cis-[(tBuNP)(2)(tBuN)(2){Li(thf)}(2)] with anhydrous yttrium trichloride or the heavier lanthanide trichlorides resulted in the corresponding cyclodiphosph(III)azane complexes [Li(thf)(4)][{(tBuNP)(2)(tBuN)(2)}LnCl(2)] (Ln=Y (1 a), Ho (1 b), Er (1 c)). The single-crystal X-ray structures showed that compounds 1 a-c consisted of ion pairs composed of a [Li(thf)(4)](+) cation and a C(2v) symmetric [{(tBuNP)(2)(tBuN)(2)}LnCl(2)](-) anion. By treating cis-[(tBuNP)(2)(tBuN)(2){Li(thf)}(2)] with anhydrous SmCl(3) in THF, the trimetallic complex [{(tBuNP)(2)(tBuN)(2)}SmCl(3)Li(2)(thf)(4)] (2) was obtained. The influence of the ionic radii of the lanthanides can be seen in the single-crystal X-ray structure of compound 2, which forms a six-membered Cl-Li-Cl-Li-Cl-Sm metallacycle. The ring adopts a boat conformation in which one chlorine atom and the samarium atom are displaced from the Cl(2)Li(2) least-square plane. Heating of the metalate complexes in toluene resulted in the extrusion of lithium chloride and the formation of the neutral dimeric metal chloride complexes of the composition [(tBuNP)(2)(tBuN)(2)LnCl(thf)](2) (Ln=Y (3 a), La (3 b) Nd (3 c), Sm (3 d)). Furthermore, treating 1 a with KNPh(2) resulted in a lithium metalate complex of the composition [Li(thf)(4)][{(tBuNP)(2)(tBuN)(2)}Y(NPh(2))(2)] (4). The coordination mode of the {(tBuNP)(2)(tBuN)(2)}(2-) ligand in 4 is different to that observed in 1 a-c, 2, and 3 a-d; instead of a symmetric eta(2) coordination of the ligand, a heterocubane-type structure is observed in the solid state. The complex [(tBuNP)(2)(tBuN)(2)NdCl(thf)] (3 c) was used as a Ziegler-Natta catalyst for the polymerization of 1,3-butadiene to poly-cis-1,4-butadiene. The observed activities of the Ziegler-Natta catalyst strongly depended upon the nature of the cocatalyst; in some case very high turnover rates and a cis selectivity of 93-94 % were observed.

N- versus P-coordination in bis(amino)cyclodiphosph(III)azane complexes of aluminum.

The reaction of the bis(amino)cyclodiphosph(III)azane, cis-{(tBuNH)(2)(PNtBu)(2)}, with AlMe(3), AlClMe(2), AlCl(2)Me, and AlCl(3) is reported. The less Lewis acidic compound AlMe(3) forms the adduct cis-[(tBuNH)(2)(PNtBu){P.(AlMe(3))NtBu}] (1), in which the aluminum atom is exclusively coordinated to one phosphorus atom. At elevated temperatures AlMe(3) undergoes migratory exchange between the two phosphorus atoms, but no methane elimination is observed. By using the more Lewis acidic compound AlClMe(2) the P-coordinated compound cis-[(tBuNH)(2)(PNtBu){P(AlClMe(2))NtBu}] (2) can be obtained at low temperatures. Compound 2 rearranges irreversibly to a product in which the AlClMe(2) group is coordinated by one exo-cyclic nitrogen atom. A concomitant 1,2-H shift from this nitrogen atom onto the phosphorus atom is observed. The N-coordinated rearrangement product slowly decomposes via a P-N bond cleavage in solution. Reaction of the even more Lewis acidic compounds AlCl(2)Me and AlCl(3) finally led to stable adducts, cis-[(tBuNH)(PNtBu)(tBuNAlCl(2)Me){P(H)NtBu}] (3), and cis-[(tBuNH)(PNtBu)(tBuNAlCl(3)){P(H)NtBu}] (4), in which the aluminum atoms are N-coordinated by a tBuN=PH unit.

Bis(phosphinimino)methanide rare earth amides: synthesis, structure, and catalysis of hydroamination/cyclization, hydrosilylation, and sequential hydroamination/hydrosilylation.

A series of yttrium and lanthanide amido complexes [Ln{N(SiHMe(2))2}2{CH(PPh(2)NSiMe(3))2}] (Ln=Y, La, Sm, Ho, Lu) were synthesized by three different pathways. The title compounds can be obtained either from [Ln{N(SiHMe(2))2}3(thf)2] and [CH(2)(PPh(2)NSiMe(3))2] or from KN(SiHMe(2))2 and [Ln{CH(PPh(2)NSiMe(3))2}Cl(2)]2, while in a third approach the lanthanum compound was synthesized in a one-pot reaction starting from K{CH(PPh(2)NSiMe(3))2}, LaCl3, and KN(SiHMe(2))2. All the complexes have been characterized by single-crystal X-ray diffraction. The new complexes, [Ln{N(SiHMe(2))2}2{CH(PPh(2)NSiMe(3))2}], were used as catalysts for hydroamination/cyclization and hydrosilylation reactions. A clear dependence of the reaction rate on the ionic radius of the center metal was observed, showing the lanthanum compound to be the most active one in both reactions. Furthermore, a combination of both reactions--a sequential hydroamination/hydrosilylation reaction--was also investigated.

A bis(phosphinimino)methanide lanthanum amide as catalyst for the hydroamination/cyclisation, hydrosilylation and sequential hydroamination/hydrosilylation catalysis.

[La[N(SiHMe2)2]2[CH(PPh2NSiMe3)2]], which was obtained via an amine elimination starting from [CH2(PPh2NSiMe3)2] and [La[N(SiHMe2)2]3(THF)2], was used as catalyst for the hydroamination/cyclisation, the hydrosilylation and the sequential hydroamination/hydrosilylation reaction.

Zirconium complexes having a chiral phosphanylamide in the co-ordination sphere.

The chiral phosphanylamido ligand, (N(CHMePh)(PPh2))-, has been introduced into co-ordination chemistry. As starting material the oily amines HN(R-*CHMePh)(PPh2)(1a) and HN(S-*CHMePh)(PPh2)(1b) were used. To reconfirm their absolute structure, 1b was oxidized with H2O2 in air to obtain HN(S-*CHMePh)(P(O)Ph2)(2) as a solid compound. The solid-state structure of 2 was established by single-crystal X-ray diffraction. The lithium salts of both enantiomers Li(N(R-*CHMePh)(PPh2))(3a) and Li(N(S-*CHMePh)(PPh2))(3b) were prepared by deprotonation reaction of 1a,b. Compounds 3a,b were further reacted with zirconocen dichloride to give the chiral metallocenes [(eta5-C5H5)2Zr(Cl)(eta2-N(R-*CHMePh)(PPh2))](4a) and [(eta5-C5H5)2Zr(Cl)(eta2-N(S-*CHMePh)(PPh2))](4b). In an alternative approach to give chiral zirconium compounds, the neutral amine 1b was reacted with [(PhCH2)4Zr] to give the enantiomeric pure complex [(PhCH2)3Zr(eta2-N(S-*CHMePh)(PPh2))](5). The solid-state structures of all zirconium complexes were determined by single-crystal X-ray diffraction.

Yttrium and lanthanide complexes with various P,N ligands in the coordination sphere: synthesis, structure, and polymerization studies.

Yttrium and lanthanide complexes with different P,N ligands in the coordination sphere have been synthesized. First the chloride complexes [{CH(PPh2NSiMe3)2}Ln{(Ph2P)2N}Cl] (Ln = Y (1 a), La (1 b), Nd (1 c), Yb (1 d)) having the bulky [CH(PPh2NSiMe3)2]- and the flexible [(Ph2P)2N]- ligands in the same molecule were prepared by three different synthetic pathways. Compounds 1 a-d can be obtained by reaction of [{[CH(PPh2NSiMe3)2]LnCl2}2] with [K(thf)nN(PPh2)2] (n = 1.25, 1.5) or by treatment of [{(Ph2P)2N}LnCl2(thf)3] with K[CH(PPh2NSiMe3)2]. Furthermore, a one-pot reaction of K[CH(PPh2NSiMe3)2] with LnCl3 and [K(thf)nN(PPh2)2] leads to the same products. Single-crystal X-ray structures of 1 a-d show that the conformation of the six-membered metallacycle (N1-P1-C1-P2-N2-Ln) which is formed by chelation of the [CH(PPh2NSiMe3)2]- ligand to the lanthanide atom is influenced by the ionic radius of the central metal atom. In solution dynamic behavior of the [(Ph2P)2N]- ligand is observed, which is caused by rapid exchange of the two different phosphorus atoms. Further reaction of 1 b with KNPh2 resulted in [{(Me3SiNPPh2)2CH}La{N(PPh2)2}(NPh2)] (2). Compounds 1 a-d and 2 are active in the ring-opening polymerization of epsilon-caprolactone and the polymerization of methyl methacrylate. In some cases high molecular weight polymers with good conversions and narrow polydispersities were obtained. In both polymerizations the catalytic activity depends on the ionic radius of the metal center.