John E. Drake

Tetraorganodichalcogenoimidodiphosphorus acids and their main group metal derivatives

Abstract The review is focused on the (XPR 2 )(YPR′ 2 )NH acids (X, Y=O, S, Se; R, R′=alkyl, aryl, OR) and their main group metal derivatives. The methods of preparation, spectroscopic studies and molecular structures of known imidodiphosphorus acids and related derivatives as well as those of inorganic and organometallic main group metal complexes containing either protonated or deprotonated imidodiphosphorus ligand moieties are systematized and discussed.

Triorganoantimony(V) complexes with internally functionallized oximes: synthetic, spectroscopic and structural aspects of [R3Sb(Br)L], [R3Sb(OH)L] and [R3SbL2], crystal and molecular structures of [Me3Sb{ONC(Me)C4H3O}2], [Me3Sb{ONC(Me)C4H3S}2], 2-OC4H3C(Me)NOH and 2-SC4H3C(Me)NOH

Triorganoantimony(V) complexes with internally functionallized oximes of the type [R3Sb{ON=C(Me)Ar}2] (1) [R=Me, Pri; Ar=C5H4N, C4H3S, C4H3O] have been prepared by the reaction of R3SbBr2 with the corresponding oximes in 1:2 molar ratio in anhydrous benzene. Treatment of 1 with one equivalent of R3SbX2 afforded a redistribution product [R3Sb(X){ON=C(Me)Ar}] (2) [X=(a):Br, (b):OH]. The species, R3Sb(OH)L, may also be obtained by the controlled hydrolysis of 1 (R=Pri; Ar=C5H4N). All of these complexes have been characterized by elemental analyses, and IR and NMR (1H and 13C) spectroscopic studies. Crystal structures of [Me3Sb{ON=C(Me)C4H3O-2}2] (3), [Me3Sb{ON=C(Me)C4H3S-2}2] (4) 2-OC4H3C(Me)=NOH (5) and 2-SC4H3C(Me)=NOH (6) are reported. The geometry around the antimony atom in 3 and 4 is distorted trigonal bipyramidal with the carbon atoms of the SbMe3 unit in equatorial positions and the two oxygen atoms of the oxime group occupying axial positions (O(1)---Sb---O(2) 171.67(12) in 3 and 169.14(13) in 4). The free oxime is clearly hydrogen bonded (H---N 2.08 A in 6) to essentially form a dimer.

Synthesis, spectroscopic and structural aspects of some tetraorganodistannoxanes with internally functionalized oxime: crystal and molecular structures of [{R2Sn(ONC(Me)py)}2O]2 (R=Bun and Et) and 2-NC5H4C(Me)NOH

Diorganotin(IV) complexes of the type [{R2Sn(ON=C(Me)py)}(2)O](2)(R = Bu-n(1), Pr-n(2), Et (3) and Me (4)) have been synthesized by the condensation reaction of R2SnO with 2-NC5H4(Me)C=NOH (5) in 1:1 molar ratio in refluxing anhydrous benzene-toluene and characterized by elemental analyses and IR and NMR (H-1, C-13 and Sn-119) spectroscopy. Two sets of Sn-119 chemical shifts are observed in the Sn-119-NMR spectra of all of these compounds indicating the presence of two types of environment around the tin atoms in solution. The crystal structures of 1, 3 and 5 have been established by single crystal X-ray diffraction, The bonding in 1 differs from that in 3 but in both structures two different environments around the tin atoms are evident with the geometry around each tin atom being that of a distorted trigonal bipyramid with alkyl groups at the equatorial positions. The structure of 5 consists of chains of molecules arising from intermolecular hydrogen bonding involving the nitrogen atom of the ring.

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.

Preparation and single-crystal characterization of manganese(II) complexes of dichalcogenoimidodiphosphinato ligands. Monomeric versus dimeric Mn[(OPPh2)(XPPh2)N]2 (X=S, O)

Abstract Manganese(II) compounds of the type Mn[(XPR2)(YPR′2)N]2 (X, Y=O, S; R, R′=Me, Ph), were prepared by metathesis reactions between MnCl2·4H2O and the alkaline salt of the corresponding ligand. IR data are consistent with the coordination of the phosphorus ligand in a deprotonated form. The ESR spectra exhibit resolved hyperfine structure only for the Mn[(OPMe2)(SPPh2)N]2 derivative. The crystal and molecular structures of Mn[(OPPh2)(YPPh2)N]2 (Y=O, S) were determined by X-ray diffractometry. The crystal of the tetraphenylthioimidodiphosphinato derivative contains monomeric, spiro-bicyclic Mn[(OPPh2)(SPPh2)N]2 units, with a distorted tetrahedral MnO2S2 core, as a result of monometallic biconnective phosphorus ligands. By contrast, in the crystal of the tetraphenylimidodiphosphinato analogue distinct [Mn{(OPPh2)2N}2]2 dimers are present, in which the MnO5 core has a trigonal bipyramidal geometry. The coordination pattern of the four imidodiphosphinato ligands differs. Two of them act as monometallic biconnective (chelating) units, leading to six-membered MnO2P2N rings. The other two ligands act as bimetallic triconnective units, which results in a fused tricyclic Mn2O4P4N2 system. The central four-membered Mn2O2 ring is slightly bent [Mn(1)O(5)O(8)/Mn(2)O(5)O(8) dihedral angle 23.9°]. The overall conformation of the [Mn{(OPPh2)2N}2]2 dimer might be described as cis, i.e. with six-membered MnO2P2N rings formed by ligands of the same type placed on the same side of the four-membered Mn2O2 ring.

First nickel(II) complexes containing tetrahedral NiO2S2 cores. The molecular structures of Ni[(OPPh2)(SPR2)N]2 (R=Ph, Me)

Abstract Ni[(OPR′2)(SPR2)N]2 complexes were obtained in good yields by reacting NiCl2·6H2O and the alkaline salts of the corresponding tetraorganomonothioimidodiphosphinic acids. All compounds were characterized by elemental analysis and IR. The molecular structure of Ni[(OPPh2)(SPR2)N]2 (R=Ph, Me) has been determined by single-crystal X-ray diffractometry. Ni[(OPPh2)-(SPPh2)N]2 (1) crystallizes in the monoclinic space group P21/c (no. 14), and Ni[(OPPh2)(SPMe2)N]2 (2) crystallizes in the triclinic space group P1 (no. 2). The crystals of both compounds contain discrete mononuclear molecules. The asymmetric ligands act as monometallic biconnective units which results in a tetrahedral NiO2S2 core.

Bis(2-{1,3-dioxan-2-yl}ethyl) telluride (L): synthesis and ligation with Pd(II) and Ru(II). Crystal structures of [Ru(p-cymene)Cl2L] and trans-[PdCl2(L)2]

Sodium telluride (Na2Te), obtained in situ by borohydride reduction of elemental tellurium, reacts with 2-(2-bromoethyl)-1,3-dioxane resulting in bis(2-{1,3-dioxan-2-yl}ethyl) telluride (L), which is isolated as an unstable viscous liquid. The potentially (Te,O-2) type of ligand L is stabilized on the formation of complexes [Ru(p-cymene)Cl2L] (1) and trans-[PdCl2(L)(2)] (2) which are characterized structurally. The Ru-Te bond length in the half sandwich compound I is 2.6559(9) A. The geometry of Pd in 2 is square planar. The Pd-Te bond length in 2 is 2.5873(2) A. 1 and 2 are the first examples of structurally characterized complexes in which potentially (Te,O-2) type ligand molecules are present, of course coordinating through Te only.

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.