Jincai Yang

Palladium (II) and platinum (II) complexes of bis(4-methoxyphenyltelluro) methane. Crystal structure of [{meso-(4-MeOC6H4Te)2CH2} (Ph2PCH2CH2PPh2) PD(II)]-(ClO4)2· 4H2O and [meso-(4-MeOC6H4Te)2CH2]Pd(II)Cl2

Abstract Palladium (II) and platinum (II) complexes of the chelating ditelluroether ligand, (MeOC6H4Te)2CH2, have been prepared and characterised by IR, UV-Vis and multinuclear (1H, 125Te{1H}, 195Pt{1H}) NMR spectroscopy and chemical analysis. [{Meso-(4-MeOC6H4Te)2CH2} (Ph2PCH2CH2PPh2) Pd(II)] (ClO42 ·4H2O, which crytallizes in the monoclinic system, space group P2 1 n (No. 14), has the cell parameters a = 19.624(7), b = 12.324(8), c = 21.497 (5) A , β = 9.227 (2)°, V = 5194(3) A , Z = 4, R = 0.0746, R w = 0.0692 and [meso-(4-MeOC6H4Te)2CH2]Pd(II) Cl2, which also crystallizes in the monoclinic system, space group P21/n (No. 14), has the cell parameters a = 7.90(2), b = 20.36(5), c = 11.44(2) A , β = 100.8(2)°, V = 1806(6) A 3 , Z = 4, R = 0.0621, R w = 0.0650 . The immediate environment about tellurium in both compounds is that of the meso invertomer and these are the first reported structures where the chelating ditelluroether had a one-carbon backbone. Only the diastereoisomer was observed in the NMR spectrum of [{meso-4-MeO-C6H4Te)2CH2} (Ph2PCH2CH2PPh2 Pd(II) ] (ClO4)2.

Crystal and molecular structures of (OPPh2)(SPPh2)NH and its sodium salt [Na(OPPh2)(SPPh2N · 2THF]2

A new method of synthesis, i.e. the reaction between Li[HN(S)PPh 2 ] and Ph 2 P(O)Cl in a diethyl ether/ n -hexane mixture, was used for the preparation of tetraphenylmonothioimidodiphosphinic acid. Its sodium salt was obtained by reacting the free acid with NaH in THF. The solid state structures of both compounds were determined by X-ray crystallography. (OPPh 2 )(SPPh 2 )NH ( 1 ) contains two independent molecules in the unit cell. Both molecules exhibit an anti conformation of the chalcogen atoms in the OPNPS system. In the crystal the molecules of 1 are associated into polymeric chains through hydrogen bonds involving only the oxygen atoms of each molecule [av. (N )H/3.O 2.09A]. the sodium salt of this acid can be considered to be built up of centrosymmetric dimers [Na(OPPh 2 )(SPPh 2 )N · 2THF] 2 ( 2 ). The O atom of the ligand unit acts as a bridging between the two Na atoms of the dimer [Na(1) O(1) 2.245(9), Na(1) O(1)′ 2.396(9)A]. In addition Na(1) is also coordinated by the S(1)′ atom [Na(1) S(1)′ 2.975(6)A] and the oxygen atoms of the two THF molecules [Na(1) O(2) 2.37(1), Na(1) O(3) 2.35(1)A]. This results in a trigonal bipyramidal geometry around sodium atoms [O(1)′ and O(3) in axial positions for Na(1), O(3) Na(1) O(1)′ 171.5(4)°], and a tricyclic system with a central planar four-membered Na 2 O 2 ring.

Triphenyltellurium(IV) dichalcogenoimidodiphosphinates containing novel six-membered TeXYP2N chelate rings. X-ray structure of Ph3Te[SPPh2) (OPPh2)N] and Ph3Te[(OPPh2)2N]

Abstract Several compounds of the type Ph3Te[(XPR2(YPR′2)N] (R=Me, Ph; R′=Me, Ph; Y=O,S) were obtained by metathesis reactions between Ph3TeCl and M[XPR2)(YPR′2)N]. Two of these (tetraphenylmonothioimidodiphosphinato)triphenyltellurium(IV), Ph3Te[(SPPh2)(OPPh2)N] (1) and (tetraphenylimidodiphosphinate)triphenyltellurium(IV), Ph3Te[(OPPh2)2N] (2) were obtained by metathesis reactions between Ph3TeCl and K[(CPPh2(OPPh2)N] or K[(OPPh2)2H], respectively. The compounds were characterized by IR and multinuclear (1H, 13C and 31P) NMR. The molecular structure of both compounds has been determined by X-ray diffractometry. Ph3Te[(SPPh2)(OPPh2)N] crystallizes in the monoclinic P2 1 c space group (No. 14) and has the cell parameters a=13.64(1), b=13.88(1), c=20.268(7) A , β=105.37(5)°, V=3699(4) A 3 and Z=4 , and Ph3Te[(OPPh2)2N] crystallizes in the monoclinic C2 c space group (No. 15) and has the cell parameters 1=20.748(6), b=12.824(5), c=28.093(6) A , β=115.48(2)°, V=7274(3) A 3 and Z=8 . Both compounds are monomeric and the immediate environment about tellurium can be described as octahedral with the apparently steochemically active lone pair occupying the axial position trans to a phenyl group from Ph3Te. The other two phenyl groups and the two long tellurium-chalcogen secondary interactuions [Te…O 2.77(1) and Te…S 3.282(4) in (1) and Te…O(1) 2.926(6) and Te…O(2) 2.654(6) A in (2) respectively] complete the equatorial plane around tellurium. As a result novel six-membered TeOSP2N and TeO2P2N inorganic chelate rings are formed. Five other compounds, Ph3Te[(SPPh2)(OPMe2)N], Ph3Te[(SPMe2)(OPPh2N], Ph3Te[(OPMe2)(OPPh2)N], Ph3Te[(SPMe2)2N] and Ph3Te[(SPMe2)(SPPh2N], were identified unequivocally but unfortunately attempts to isolate them failed due to decomposition. The reaction mixtures were investigated by multinuclear (1H, 11C and 31P) NMR spectroscopy.

The first crystal structures of mixed chalcogen derivatives SnR2[(OPPh2)(SPPh2)N]2(R = Me or Ph)

The compounds SnR2[(OPPh2)(SPPh2)N]2(R = Me, Bun, CH2Ph or Ph) were prepared by metathesis reactions between SnR2Cl2 and K[(OPPh2)(SPPh2)N] in toluene. Reactions between SnR3Cl (R = Me or Ph) and K[(OPPh2)(SPPh2)N](1 : 1 molar ratio) in boiling toluene also produced the dimethyl- and diphenyltin(IV) derivatives as redistribution products. The same reactions in chloroform at room temperature afford the corresponding triorganotin(IV) compounds. The compounds were characterized by means of IR and multinuclear NMR spectroscopy. The crystal and molecular structures of SnR2[(OPPh2)(SPPh2)N]2(R = Me 1 or Ph 2) derivatives were determined by X-ray diffractometry. Both compounds exhibit very similar spirobicyclic structures, with the tin atom as spiro atom. The ligand moieties are monometallic biconnective (bidentate) through both oxygen and sulfur atoms [Sn–S 2.758(1) in 1 and 2.680(4) in 2, Sn–O 2.199(2) in 1 and 2.189(5)A in 2]. The co-ordination geometry around the central metal atom is octahedral, with C–Sn–C, O–Sn–O (trans) and S–Sn–S (trans) angles of 180°. The conformation of the six-membered SnOSP2N inorganic rings is twisted boat.

Metal-oxygen versus metal-sulfur bonding of the ambident monothiophosphinato ligand in some triphenylmeta(IV) derivatives, Ph3M[OSPR2] (M = Ge, Sn, Pb). Crystal structures of Ph3Ge[O(S)PPh2] and [Ph2Sn{O(S)PPh2} (μ-OH)]2

Abstract Diorganomonothiophosphinato-triphenylmetal(IV) derivatives, Ph 3 M(OSPR @ ) (M = Ge, Sn, Pb; R = Me, Et, Ph), were prepared and investigated. The IR and multinuclear ( 1 H, 13 C, 31 P) NMR spectra are discussed in relation to the MO and/or MS bonding of the ambident OSPR 2 − ligand. The crystal and molecular structures of Ph 3 Ge[O(S)PPh 2 ] ( 1 ) and [Ph 2 Sn{O(S)PPh 2 } (μ-OH)] 2 ( 2 ) were determined by X-ray diffractometry. The asymmetric unit for Ph 3 Ge[O(S)PPh 2 ] contains two independent molecules. The monothiophosphinato group is bonded to germanium only through oxygen (av. GeO 1.826, Ge···S 3.892 A), leading to a tetrahedral coordination around the germanium atom. The crystal of [Ph 2 Sn{O(S)PPh 2 } (μ-OH)] 2 consists of dimeric units built up through SnOSn bridges involving the oxygen atom of the hydroxy groups. The monothiophosphinato group is again monodentate [Sn(1)O(1) 2.089(3), Sn(1)···S(1) (non-bonding) 4.164 A] and the coordination geometry around tin is trigonal bipyramidal, with the O(1) atom of the phosphorus ligand and the O(2′) atome of a bridging hydroxy group in axial positions.

NEW VERSATILE ORGANOPHOSPHORUS LIGANDS. CRYSTAL AND MOLECULAR STRUCTURES OF ISOMERIC P, P-DIMETHYL-P′,P′-DIPHENYL-P-THIOIMIDODIPHOSPHINIC AND P,P-DIMETHYL-P′,P′-DIPHENYL-P′-THIOIMIDODIPHOSPHINIC ACIDS

Abstract The synthesis of isomeric (SPMe2)(OPPh2)NH 1 and (OPMe2)(SPPh2)NH 2 from Li[HN(S)PR2] and R′2P(O)Cl, as well as of their K and Na salts, are presented. The compounds were characterized by means of IR and multinuclear NMR spectroscopy. The crystal and molecular structure of both free acids was determined using X-ray diffractometry. Compound 1 crystallizes in monoclinic space group P21/n, a = 16.798(6) A, b = 17.526(8) A, c = 18.095(7) A, β =114.72(2)°, Z = 12, and the unit cell contains three independent molecules. Compound 2 crystallizes in orthorhombic space group Fdd2, a = 1.5.072(7) A, b = 43.078(6) A, c = 9.912(8) A, Z = 16. In both compounds the molecular units are associated into polymeric chains through N-H-O [1.96 A (mean) in 1, and 1.8 A in 2] hydrogen bonds, which involve only the oxygen atom of each molecule. The conformation of the SPNPO system is discussed.

The X-ray crystal structure of (diphenylmonothiophosphinato)triphenyltin(IV), [Ph3Sn(OSPPh2)]n, exhibiting a polymeric chain supramolecular self-assembly

The molecular structure of (diphenylmonothiophosphinato)triphenyltin(IV) was determined by X-ray diffractometry. The diphenylmonothiophosphinato ligand is bimetallic biconnective leading to a polymeric [SnSPO] n chain: Sn(1) S(1) [2.785(3)A] and Sn(1) O(1′) [2.172(6)A]. The coordination geometry about tin is trigonal bipyramidal with chalcogen atoms in apical positions [O(1′) Sn(1) S(1) 176.6(2)°] and carbon atoms of the phenyl groups attached to the metal in equatorial positions. The bridging pattern of the ambident monothio ligand is discussed in terms of partial bond orders and compared with those observed in other related organotin(IV) derivatives.

DI-μ-CHLORO-BIS[l,2-BIS(DIPHENYLPHOSPHINO)-ETHANEPALLADIUM(II)]: SYNTHESIS AND CRYSTAL STRUCTURE

Abstract On reacting 1,2-bis(diphenylphosphino)ethanedichloropalladium(II) with equimolar amount of silver perchlorate, a binuclear complex, di-μ-chloro-bis[1,2-bis(diphenylphosphino)ethane-palladium(II)] (1) is formed. The crystal structure of 1 has been solved. It crystallizes with two chloroform molecules. Chloro bridges are symmetrical and normal (Pd-Cl∼2.414(3) A). The immediate environment around palladium is slightly distorted square planar and the P-Pd-P angle is ∼85°. IR bands at 290 and 270cm−1 are observed for the chloro-bridged core of the complex.

REACTION OF TETRACLOROPALLADATE (II) WITH BIS(2-CHLOROETHYL)AMINE: SELECTIVE FORMATION OF A trans ISOMER. CRYSTAL STRUCTURE OF trans-[PdCl2{NH(CH2CH2Cl)2}2]

Abstract On reacting [PbCl4]2- with bis(2-chloroethyl)amine, trans-[PdCl2{NH(CH2CH2Cl)2}2] (1) results selects selectively in high yield (∼80%). The structure of 1 has been solved by X-ray diffraction methods. The immediate environment about palladium is slightly distorted square planar, Pd-Cl bond lengths (2.297(1)/2.999(i)A) are in accordance with the trans-influence of various co-ligands. The Pd-N bond length is intermediate between Pd-NH3 and Pd-NMe2 bond distances. Attempts to substitute the Cl atom of the alkyl chain by nucleophile ArTe-leads to dissociaton of the complex resulting in Pd(TeAr)2 and NH(CH2CH2TeAr)2.