Variable Bonding Modes of Pyrimidine‐2‐thione in PdII/PtII Complexes [M(η2‐N,S‐pymS)(η1‐S‐pymS)(PPh3)] and [M(η1‐S‐pymS)2(L‐L)] (L‐L = dppm,dppe)

Reactions of pyrimidine‐2‐thione (HpymS) with Pd^II/Pt^IV salts in the presence of triphenyl phosphine and bis(diphenylphosphino)alkanes, Ph₂P‐(CH₂)_m‐PPh₂ (m = 1, 2) have yielded two types of complexes, viz. a) [M(η²‐N, S‐ pymS)(η¹‐S‐ pymS)(PPh₃)] (M = Pd, 1 ; Pt, 2 ), and (b) [M(η¹‐S‐pymS)₂(L‐L)] {L‐L, M = dppm (m = 1) Pd, 3 ; Pt, 4 ; dppe (m = 2), Pd, 5 ; Pt, 6 }. Complexes have been characterized by elemental analysis (C, H, N), NMR spectroscopy (¹H, ¹³C, ³¹P), and single crystal X‐ray crystallography ( 1 , 2 , 4 , and 5 ). Complexes 1 and 2 have terminal η¹‐S and chelating η²‐N, S‐modes of pymS⁻, while other Pd/Pt complexes have only terminal η¹‐S modes. The solution state ³¹P NMR spectral data reveal dynamic equilibrium for the complexes 3 , 5 and 6 , whereas the complexes 1 , 2 and 4 are static in solution state.     

Thiosemicarbazonates of Ruthenium(II): Crystal Structures of [Bis(triphenylphosphine)][bis(N‐phenyl‐pyridine‐2‐carbaldehyde Thiosemicarbazonato)]ruthenium(II) and [Bis(diphenylphosphino)butane][bis(salicylaldehyde Thiosemicarbazonato)]ruthenium(II)

Reaction of RuCl₂(PPh₃)₃ with N‐Phenyl‐pyridine‐2‐carbaldehyde thiosemicarbazone (C₅H₄N–C²(H)=N³‐N²H–C¹(=S)N¹HC₆H₅, Hpytsc‐NPh) in presence of Et₃N base led to loss of ‐N²H‐proton and yielded the complex [Ru(pytsc‐NPh)₂(Ph₃P)₂] ( 1 ). Similar reactions of precursor RuCl₂[(p‐tolyl)₃P]₃ with a series of thiosemicarbazone ligands, viz. pyridine‐2‐carbaldehyde thiosemicarbazone (Hpytsc), salicylaldehyde thiosemicarbazone (H₂stsc), and benzaldehyde thiosemicarbazone (Hbtsc), have yielded the complexes, [Ru(pytsc)₂{(p‐tolyl)₃P}₂] ( 2 ), [Ru(Hstsc)₂{(p‐tolyl)₃P}]₂ ( 3 ), and [Ru(btsc)₂{(p‐tolyl)₃P}₂] ( 4 ), respectively. The reactions of precursor Ru₂Cl₄(dppb)₃ {dppb = Ph₂P–(CH₂)₄–PPh₂} with H₂stsc, Hbtsc, furan‐2‐carbaldehyde thiosemicarbazone (Hftsc) and thiophene‐2‐carbaldehyde thiosemicarbazone (Httsc) have formed complexes of the composition, [Ru(Hstsc)₂(dppb)] ( 5 ), [Ru(btsc)₂(dppb)] ( 6 ), [Ru(ftsc)₂(dppb)] ( 7 ), and [Ru(ttsc)₂(dppb)] ( 8 ). The complexes have been characterized by analytical data, IR, NMR (¹H, ³¹P) spectroscopy and X‐ray crystallography ( 1 and 5 ). The proton NMR confirmed loss of –N²H– proton in all the compounds, and ³¹P NMR spectra reveal the presence of equivalent phosphorus atoms in the complexes. In all the compounds, thiosemicarbazone ligands coordinate to the Ru^II atom via hydrazinic nitrogen (N²) and sulfur atoms. The arrangement around each metal atom is distorted octahedral with cis:cis:trans P, P:N, N:S, S dispositions of donor atoms.     

Synthesis,spectroscopy and structure of cis,cis,trans:N,N;P,P;S,S-[bis(triphenylphosphine)] [bis(pyrimidine-2-thiolato)]ruthenium(II)

Reaction of RuCl₂(PPh₃)₃with pyrimidine-2-thione (HpymS) in a 1:2?mol ratio in dry benzene in the presence of triethylamine as base yielded a complex of stoichiometry [Ru(pymS)₂(PPh₃)₂] (1). This has been characterized using analytical data and IR, ¹H, ¹³C and ³¹P NMR spectroscopy. ¹H NMR confirmed the deprotonation of HpymS. ³¹P NMR spectra showed a single peak confirming equivalent P atoms. Complex 1 crystallizes in space group Pī and HpymS acts as a η²-N,S-deprotonated bidentate anionic ligand. The coordination geometry around the Ru center is distorted octahedral with cis dispositions of P atoms, as well as two N atoms of pymS^– and trans S atoms of pymS^–. Important bond distances and angles are: Ru–N, 2.119(2), 2.106(2); Ru–S, 2.4256(8), 2.4413(8); and Ru–P, 2.3266(7), 2.3167(7)?Å; P(2)–Ru(1)–P(1), 96.07(3); N(21)–Ru(1)–N(11), 83.46(9); and S(1)–Ru(1)–S(2), 153.02(3)°.     

1, 9‐Dihydro‐purine‐6‐thione Derivatives of the d8–d10 Metal Ions (PdII,PtII, and CuI): Synthesis,Spectroscopy, and Structures

Reaction of 1, 9‐dihydro‐purine‐6‐thione (puSH₂) in presence of aqueous sodium hydroxide with PdCl₂(PPh₃)₂ suspended in ethanol formed [Pd(κ²‐N⁷,S‐puS)(PPh₃)₂] ( 1 ). Similarly, complexes [Pd(κ²‐N⁷,S‐puS)(κ²‐P, P‐L‐L)] ( 2 – 4 ) {L‐L = dppm (m = 1) ( 2 ), dppp (m = 3) ( 3 ), dppb (m = 4) ( 4 )} were prepared using precursors the [PdCl₂(L‐L)] {L‐L = Ph₂P–(CH₂)_m–PPh₂}. Reaction of puSH₂ suspended in benzene with platinic acid, H₂PtCl₆, in ethanol in the presence of triethylamine followed by the addition of PPh₃ yielded the complex [Pt(κ²‐N⁷,S‐puS)(PPh₃)₂] ( 5 ). Complexes [Pt(κ²‐N⁷,S‐puS)(κ²‐P, P‐L‐L)] ( 6 – 8 ) {L‐L = dppm ( 6 ), dppp ( 7 ), dppb ( 8 )} were prepared similarly. The 1, 9‐dihydro‐purine‐6‐thione acts as N⁷,S‐chelating dianion in compounds 1 – 8 . The reaction of copper(I) chloride [or copper(I) bromide] in acetonitrile with puSH₂ and the addition of PPh₃ in methanol yielded the same product, [Cu(κ²‐N⁷,S‐puSH)(PPh₃)₂] ( 9 ), in which the halogen atoms are removed by uninegative N, S‐chelating puSH^– anion. However, copper(I) iodide did not lose iodide and formed the tetrahedral complex, [CuI(κ¹‐S‐puSH₂)(PPh₃)₂] ( 10 ), in which the thio ligand is neutral. These complexes were characterized with the help of elemental analysis, NMR spectroscopy (¹H, ³¹P), and single‐crystal X‐ray crystallography ( 3 , 7 , 8 , 9 , and 10 ).     

The Synthesis by Decarboxylation Reactions and Crystal Structures of 1, n–Bis(diphenylphosphino)alkane(pentafluorophenyl)‐platinum(II) Complexes

Decarboxylation reactions between the complexes cis–[PtCl₂L] (L = 1, n–bis(diphenylphosphino)–ethane (n = 2, dppe), –propane (n = 3, dppp) or –butane (n = 4, dppb)) and thallium(I) pentafluorobenzoate in pyridine give cis–[PtCl(C₆F₅)L] and cis–[Pt(C₆F₅)₂L] complexes in high yields with short reaction times. X–ray crystal structures of cis–[PtCl(C₆F₅)(dppe)] · 0.5 C₅H₅N, cis–[PtCl(C₆F₅)(dppp)], cis–[PtCl(C₆F₅)(dppb)] · C₃H₆O, cis–[Pt(C₆F₅)₂L] (L = dppe, dppp and dppb) and the reactants cis–[PtCl₂(dppp)] (as a CH₂Cl₂ solvate) and cis–[PtCl₂(dppb)] show monomeric structures with chelating diphosphine ligands in all cases rather than dimers with bridging diphosphines. ³¹P NMR data are consistent with these structures in solution.     

N‐(2‐Hydroxyethyl)‐N‐methyldithiocarbamato Complexes of Nickel(II) with Phosphorus Donor Ligands

Planar nickel(II) complexes involving N‐(2‐Hydroxyethyl)‐N‐methyldithiocarbamate, such as [NiX(nmedtc)(PPh₃)] (X = Cl, NCS; PPh₃ = triphenylphosphine), and [Ni(nmedtc)(P‐P)]ClO₄(P‐P = 1,1‐bis(diphenylphosphino)methane(dppm); 1,3‐bis(diphenylphosphino)propane (1,3‐dppp); 1,4‐bis(diphenylphosphino)butane(1,4‐dppb) have been synthesized. The complexes have been characterized by elemental analyses, IR and electronic spectroscopies. The increased νC–N value in all the complexes is due to the mesomeric drift of electrons from the dithiocarbamate ligands to the metal atom. Single crystal X‐ray structure of [Ni(nmedtc)(1,3‐dppp)]ClO₄·H₂O is reported. In the present 1,3‐dppp chelate, the P–Ni–P angle is higher than that found in 1,2‐bis(diphenylphosphino)ethane‐nickel chelates and lower than 1,4‐bis(diphenylphosphino)butane‐nickel chelates, as a result of presence of the flexible propyl back bone connecting the two phosphorus atoms of the complex.     

Tin(II) Halide Insertion or Halogen Exchange in the Reactions of Dihaloplatinum(II) Complexes with Tin(II) Halide

Reactions of SnCl₂ with the complexes cis‐[PtCl₂(P₂)] (P₂=dppf (1,1′‐bis(diphenylphosphino)ferrocene), dppp (1,3‐bis(diphenylphosphino)propane=1,1′‐(propane‐1,3‐diyl)bis[1,1‐diphenylphosphine]), dppb (1,4‐bis(diphenylphosphino)butane=1,1′‐(butane‐1,4‐diyl)bis[1,1‐diphenylphosphine]), and dpppe (1,5‐bis(diphenylphosphino)pentane=1,1′‐(pentane‐1,5‐diyl)bis[1,1‐diphenylphosphine])) resulted in the insertion of SnCl₂ into the Pt? Cl bond to afford the cis‐[PtCl(SnCl₃)(P₂)] complexes. However, the reaction of the complexes cis‐[PtCl₂(P₂)] (P₂=dppf, dppm (bis(diphenylphosphino)methane=1,1′‐methylenebis[1,1‐diphenylphosphine]), dppe (1,2‐bis(diphenylphosphino)ethane=1,1′‐(ethane‐1,2‐diyl)bis[1,1‐diphenylphosphine]), dppp, dppb, and dpppe; P=Ph₃P and (MeO)₃P) with SnX₂ (X=Br or I) resulted in the halogen exchange to yield the complexes [PtX₂(P₂)]. In contrast, treatment of cis‐[PtBr₂(dppm)] with SnBr₂ resulted in the insertion of SnBr₂ into the Pt? Br bond to form cis‐[Pt(SnBr₃)₂(dppm)], and this product was in equilibrium with the starting complex cis‐[PtBr₂(dppm)]. Moreover, the reaction of cis‐[PtCl₂(dppb)] with a mixture SnCl₂/SnI₂ in a 2 : 1 mol ratio resulted in the formation of cis‐[PtI₂(dppb)] as a consequence of the selective halogen‐exchange reaction. ³¹P‐NMR Data for all complexes are reported, and a correlation between the chemical shifts and the coupling constants was established for mono‐ and bis(trichlorostannyl)platinum complexes. The effect of the alkane chain length of the ligand and Sn^II halide is described.     

Zur Reaktivität von dinuklearen Platina‐β‐diketonen gegenüber Phosphanen: Diacetylplatin(II)‐Komplexe und mononukleare Platina‐β‐diketone

The Reactivity of Dinuclear Platina‐β‐diketones with Phosphines: Diacetylplatinum(II) Complexes and Mononuclear Platina‐β‐diketones Addition of mono‐ and bidentate phosphines or of AsPh₃ to the platina‐β‐diketone [Pt₂{(COMe)₂H}₂(μ‐Cl)₂] ( 1 ) followed by the addition of NaOMe at ?70 °C resulted in the formation of diacetyl platinum(II) complexes cis‐[Pt(COMe)₂L₂] (L = PPh₃, 2a ; P(4‐FC₆H₄)₃, 2b ; PPh₂(4‐py), 2c ; PMePh₂, 2d ; AsPh₃, 2d ) and [Pt(COMe)₂(L??L)] (L??L = dppe, 3b ; dppp, 3c ), respectively. The analogous reaction with dppm afforded the dinuclear complex cis‐[{Pt(COMe)₂}₂(μ‐dppm)₂] ( 4 ) that reacted in boiling acetone yielding [Pt(COMe)₂(dppm)] ( 3a ). The reactions 1 → 2 / 3 were found to proceed via thermally highly unstable cationic mononuclear platina‐β‐diketone intermediates [Pt{(COMe)₂H}L₂]⁺ and [Pt{(COMe)₂H}(L??L)]⁺, respectively, that could be isolated as chlorides for L??L = dppe ( 5a ) and dppp ( 5b ). The reversibility of the deprotonation of type 5 complexes with NaOMe yielding type 3 complexes was shown by the protonation of the diacetyl complex 3b with HBF₄ yielding the platina‐β‐diketone [Pt{(COMe)₂H}(dppe)](BF₄) ( 5c ). All compounds were fully characterized by means of NMR and IR spectroscopies, and microanalyses. X‐ray diffraction analysis was performed for the complex cis‐[Pt(COMe)₂(PPh₃)₂]·H₂O·CHCl₃ ( 2a ·H₂O·CHCl₃).     

The Structure of cis‐[Chloro(dimethylsulfoxide)bis(1, 10‐phenanthroline)ruthenium(II)]‐tetraphenylborate, [RuCl(DMSO)(1, 10‐phen)2][BPh4]

The complex cis‐[RuCl(DMSO)(phen)₂]BPh₄, where DMSO is dimethylsulfoxide and phen is 1, 10‐phenanthroline, crystallizes in the monoclinic space group P2₁/c with a = 19.505(4), b = 10.045(2), c = 21.199(4) Å, β = 90.137(4)°, V = 4153(2) ų, Z = 4, D_calc = 1.430 g cm^—3. The ruthenium coordination geometry is that of a slightly distorted octahedron with a cis‐RuN₄ClS arrangement of the ligand donor atoms. The Ru—Cl distance is 2.421(1) Å and the Ru—S distance 2.250(2) Å. The four Ru—N distances are 2.057(6), 2.066(4), 2.073(4), and 2.086(4) Å with the Ru—N bond trans to Cl the second shortest and the Ru—N bond trans to S the longest one.     

Bis(diphenylphosphano)alkan- und 1-(Diphenylphosphano)-2-(2-pyridino)ethan-N-Arylsulfinylamin-Nickel(0)-Komplexe

Bis(diphenylphosphano)alkane- and 1-Diphenylphosphano-2-(2-pyridino)ethane-N-arylsulfinylamine Nickel(0) Complexes Synthesis and properties of the bis(diphenylphosphano)alkane-N-phenyl-sulfinylamine-nickel(0) complexes [Ni{Ph₂P(CH₂)_nPPh₂}(PhNSO)] (n = 2 dppe, n = 3 dppp, n = 4 dppb) as well as of the 1-(diphenylphosphano)-2-(2-pyridino)ethane nickel(0) complexes [Ni(dpppe)₂], [Ni(dpppe)(p-TolNSO)] and [Ni(dpppe)(PPh₃)₂] are described. These compounds have been characterized by i. r. and ³¹P n.m.r. spectroscopy. The N-arylsulfinylamine ligands are η²-(N, S)-side on coordinated.     

Syntheses and Structures of Ruthenium(II) N,S‐Heterocyclic Carbene Diphosphine Complexes and their Catalytic Activity towards Transfer Hydrogenation

Phosphine exchange of [Ru^IIBr(MeCOO)(PPh₃)₂(3‐RBzTh)] (3‐RBzTh=3‐benzylbenzothiazol‐2‐ylidene) with a series of diphosphines (bis(diphenylphosphino)methane (dppm), 1,2‐bis(diphenylphosphino)ethylene (dppv), 1,1′‐bis(diphenylphosphino)ferrocene (dppf), 1,4‐bis(diphenylphosphino)butane (dppb), and 1,3‐(diphenylphosphino)propane (dppp)) gave mononuclear and neutral octahedral complexes [RuBr(MeCOO)(η²‐P₂)(3‐RBzTh)] (P₂=dppm ( 2 ), dppv ( 3 ), dppf ( 4 ), dppb ( 5 ), or dppp ( 6 )), the coordination spheres of which contained four different ligands, namely, a chelating diphosphine, carboxylate, N,S‐heterocyclic carbene (NSHC), and a bromide. Two geometric isomers of 6 ( 6a and 6 b ) have been isolated. The structures of these products, which have been elucidated by single‐crystal X‐ray crystallography, show two structural types, I and II, depending on the relative dispositions of the ligands. Type I structures contain a carbenic carbon atom trans to the oxygen atom, whereas two phosphorus atoms are trans to bromine and oxygen atoms. The type II system comprises a carbene carbon atom trans to one of the phosphorus atoms, whereas the other phosphorus is trans to the oxygen atom, with the bromine trans to the remaining oxygen atom. Complexes 2 , 3 , 4 , and 6a belong to type I, whereas 5 and 6 b are of type II. The kinetic product 6 b eventually converts into 6a upon standing. These complexes are active towards catalytic reduction of para‐methyl acetophenone by 2‐propanol at 82 °C under 1 % catalyst load giving the corresponding alcohols. The dppm complex 2 shows the good yields (91–97 %) towards selected ketones.     

Bis[N‐(2‐hydroxy­ethyl)‐β‐alaninato]copper(II)

The Cu^II ion in the title complex, [Cu(C₅H₁₀NO₃)₂] or [Cu(He‐ala)₂] [He‐ala = N‐(2‐hydroxy­ethyl)‐β‐alaninate], resides at the inversion centre of a square bipyramid comprised of two facially arranged tridentate He‐ala ligands. Each He‐ala ligand binds to a Cu^II ion by forming one six‐membered β‐alaninate chelate ring in a twist conformation and one five‐membered ethanol­amine ring in an envelope conformation, with Cu—N = 2.017 (2) Å, Cu—O_COO = 1.968 (1) Å and Cu—O_OH = 2.473 (2) Å. The [Cu(He‐ala)₂] mol­ecules are involved in a network of O—H⋯O and N—H⋯O hydrogen bonds, forming layers parallel to the (10) plane. The layers are connected into a three‐dimensional structure by van der Waals inter­actions, so that the mol­ecular centres form pseudo‐face‐centered close packing.     

Aktivierung von Schwefelkohlenstoff an Trirutheniumclustern: Synthese und Kristallstruktur von [Ru3(CO)5(μ‐H)2(μ‐PCy2)(μ‐Ph2PCH2PPh2){μ‐η2‐PCy2C(S)}(μ3‐S)] und [Ru3(CO)5(CS)(μ‐H)(μ‐PtBu2)(μ‐PCy2)2(μ3‐S)]

Activation of Carbon Disulfide on Triruthenium Clusters: Synthesis and X‐Ray Crystal Structure Analysis of [Ru₃(CO)₅(μ‐H)₂(μ‐PCy₂)(μ‐Ph₂PCH₂PPh₂){μ‐η²‐PCy₂C(S)}(μ₃‐S)] and [Ru₃(CO)₅(CS)(μ‐H)(μ‐P^tBu₂)(μ‐PCy₂)₂(μ₃‐S)] [Ru₃(CO)₆(μ‐H)₂(μ‐PCy₂)₂(μ‐dppm)] ( 1 ) (dppm = Ph₂PCH₂PPh₂) reacts under mild conditions with CS₂ and yields by oxidative decarbonylation and insertion of CS into one phosphido bridge the opened 50 VE‐cluster [Ru₃(CO)₅(μ‐H)₂(μ‐PCy₂)(μ‐dppm){μ‐η²‐PCy₂C(S)}(μ₃‐S)] ( 2 ) with only two M–M bonds. The compound 2 crystallizes in the triclinic space group P 1 with a = 19.093(3), b = 12.2883(12), c = 20.098(3) Å; α = 84.65(3), β = 77.21(3), γ = 81.87(3)° and V = 2790.7(11) ų. The reaction of [Ru₃(CO)₇(μ‐H)(μ‐P^tBu₂)(μ‐PCy₂)₂] ( 3 ) with CS₂ in refluxing toluene affords the 50 VE‐cluster [Ru₃(CO)₅(CS)(μ‐H)(μ‐P^tBu₂)(μ‐PCy₂)₂(μ₃‐S)] ( 4 ). The compound cristallizes in the monoclinic space group P 2₁/a with a = 19.093(3), b = 12.2883(12), c = 20.098(3) Å; β = 104.223(16)° and V = 4570.9(10) ų. Although in the solid state structure one elongated Ru–Ru bond has been found the complex 4 can be considered by means of the ³¹P‐NMR data as an electron‐rich metal cluster.     

Synthese und Strukturen neuer selenido‐ und selenolatoverbrückter Kupfercluster: [Cu38Se13(SePh)12(dppb)6] (1), [Cu(dppp)2][Cu25Se4(SePh)18(dppp)2] (2), [Cu36Se5(SePh)26(dppa)4] (3), [Cu58Se16(SePh)24(dppa)6] (4) und [Cu3(SeMes)3(dppm)] (5)

Syntheses and Crystal Structures of new Selenido‐ and Selenolato‐bridged Copper Clusters: [Cu₃₈Se₁₃(SePh)₁₂(dppb)₆] (1), [Cu(dppp)₂][Cu₂₅Se₄(SePh)₁₈(dppp)₂] (2), [Cu₃₆Se₅(SePh)₂₆(dppa)₄] (3), [Cu₅₈Se₁₆(SePh)₂₄(dppa)₆] (4), and [Cu₃(SeMes)₃(dppm)] (5) The reactions of copper(I) chloride or copper(I) acetate with monodentate phosphine ligands (PR₃; R = organic group) and Se(SiMe₃)₂ have already lead to the formation of CuSe clusters with up to 146 copper and 73 selenium atoms. If the starting materials and the bidentate phosphine ligands (Ph₂P–(CH₂)_n–PPh₂, n = 1: dppm, n = 3: dppp, n = 4: dppb; Ph₂P–C≡C–PPh₂: dppa) and silylated chalcogen derivates are changed (RSeSiMe₃; R = Ph, Mes) a series of new CuSe clusters can be synthesized. From single crystal X‐ray structure analysis one can characterise [Cu₃₈Se₁₃(SePh)₁₂(dppb)₆] ( 1 ), [Cu(dppp)₂] · [Cu₂₅Se₄(SePh)₁₈(dppp)₂] ( 2 ), [Cu₃₆Se₅(SePh)₂₆(dppa)₄] ( 3 ), [Cu₅₈Se₁₆(SePh)₂₄(dppa)₆] ( 4 ) and [Cu₃(SeMes)₃(dppm)] ( 5 ). In this new class of CuSe clusters, compounds 1 and 4 possess a spherical cluster skeleton, wheras 2 and 3 have a layered cluster core.     

The Synthesis and Structure of Hexakis(dimethylphenylphosphonite)ruthenium(II) bis[tetraphenylborate(–1)]

Abstract . Treatment of the hydrazine salt [Ru(COD)(H₂NNH₂)₄][BPh₄]₂ with excess of P(OMe)₂Ph in acetone gave a homoleptic complex trans‐[Ru{P(OMe)₂Ph}₆][BPh₄]₂, which was characterized by IR, ³¹P{¹H}, ¹³C{¹H}, and ¹H NMR spectroscopy, elemental analysis, and X‐ray crystallography. The ruthenium in the complex has distorted octahedral coordination arrangement and bonded to all the six P(OMe)₂Ph molecules through the phosphorus atoms.     

Partially oxidized ruthenium phosphine thiol­ates: [Ru(pySO2)0.33(pyS)1.67(dppe)] and [Ru(pySO2)0.355(pyS)1.645(dppp)]

The crystal structures of [1,3‐bis­(diphenyl­phosphino)ethane‐κ²P,P′](pyridine‐2‐sulfinato‐κ²N,S)(pyridine‐2‐thiol­ato‐κ²N,S)ruthenium(II), [Ru(C₅H₄NO₂S)_0.33(C₅H₄NS)_1.67(C₂₆H₂₄P₂)] or [Ru(pySO₂)_1−x(pyS)_1+x(dppe)] (x = 0.67), (I), and [1,3‐bis­(diphenyl­phosphino)propane‐κ²P,P′](pyridine‐2‐sulfinato‐κ²N,S)(pyridine‐2‐thiol­ato‐κ²N,S)ruthenium(II), [Ru(C₅H₄NO₂S)_0.355(C₅H₄NS)_1.645(C₂₇H₂₆P₂)] or [Ru(pySO₂)_1−x(pyS)_1+x(dppp)] (x = 0.645), (II), are composed of neutral distorted octa­hedral Ru^II complexes with chelating pyridine‐2‐thiol­ate, pyridine‐2‐sulfinate and biphosphine ligands. The S atoms are trans to each other, while pairs of P and N atoms are in cis positions. Partial double‐bond character is observed for C—S. The crystal packing consists of monolayers stabilized by C—H⋯O and C—H⋯S inter­actions, and is affected by the alkyl‐chain lengths.     

Palladium(II) and Platinum(II) Complexes with Bisphosphanes, [S2C=C(CN)2]2– and [Se2C=C(CN)2]2– as Chelating Ligands

The palladium(II) and platin(II) 1, 1‐dicyanoethylene‐2, 2‐dithiolates [(L–L)M{S₂C=C(CN)₂}] (M = Pd: L–L = dppm, dppe, dcpe, dpmb; M = Pt: dppe, dcpe, dpmb) were prepared either from[(L–L)MCl₂] and K₂[S₂C=C(CN)₂] or from [(PPh₃)₂M{S₂C=C(CN)₂}] and the bisphosphane. Moreover, [(dppe)Pt{S₂C=C(CN)₂}]was obtained from [(1, 5‐C₈H₁₂)Pt{S₂C=C(CN)₂}] and dppeby ligand exchange. The 1, 1‐dicyanoethylene‐2, 2‐diselenolates[(dppe)M{Se₂C=C(CN)₂}] (M = Pd, Pt) were prepared from[(dppe)MCl₂] and K₂[Se₂C=C(CN)₂]. The oxidation potentials of the square‐planar palladium and platinum complexes were determined by cyclic voltammetry. The reaction of [(dcpe)Pd(S₂C=O)] with TCNE led to a ligand fragment exchange and gave the 1, 1‐dicyanoethylene‐2, 2‐dithiolate [(dcpe)Pd{S₂C=C(CN)₂}] in good yield.     

X‐Ray Photoelectron Spectral Studies on Planar NiS4 and NiS2P2 Chromophores. Single Crystal X‐Ray Structural Study on [1, 4‐Bis(diphenylphosphino‐k,P, P')butane](piperidinecarbodithioato‐S,S')‐Nickel(II) Perchlorate

X‐ray photoelectron spectral study was made on the complexes Ni(nmedtc)₂( 1 ), [Ni(nmedtc)(PPh₃)₂]ClO₄( 2 ), [Ni‐(nmedtc)(dppe)]BPh₄( 3 ) (where nmedtc = N‐methyl, N‐ethanoldithiocarbamate, dppe = 1, 2‐bis(diphenylphosphino)ethane). The nickel 2p_3/2 binding energy values for chelated and free phosphine complexes are 854.0 and 854.1 eV which are significantly different from Ni2p_3/2 BE value of NiS₄ chromophore, indicating the relative dearth of electron density on Ni in NiS₂P₂ chromophores. The presence of two phosphine groups in NiS₂P₂ chromophore alleviates the electron density on the metal atom. More electron density is being pulled away from the metal atom in chelates than in the PPh₃ analogue. This observation is in line with solution studies by cyclic voltammetry. A one‐electron reduction potential was observed to be the minimum for NiS₂P₂ chromophores compared to the others. Also the crystal structure of the complex [Ni(pipdtc)(1, 4‐dppb)]ClO₄ (pipdtc^‐ = piperidinecarbodithioato anion, 1, 4‐dppb = bis(diphenylphosphino)butane) prepared by the reaction between Ni(pipdtc)₂, NiCl₂�6₂2O, and 1, 4‐dppb in CH₃CN‐CH₃OH is reported.     

cis‐[1,4‐Bis(di­phenyl­phosphino)­butane](μ‐tetra­thio­tungstato)­palladium(II) N,N′‐di­methyl­form­amide hemisolvate hemihydrate

In the title compound, [1,4‐bis(di­phenyl­phosphino)­butane‐2κ²P,P′]­di‐μ‐thio‐1:2κ⁴S‐di­thio‐1κ²S‐palladium(II)­tung­sten(VI) N,N′‐di­methyl­form­amide hemisolvate hemihydrate, [PdWS₄­(C₂₈H₂₈P₂)]·0.5C₃H₇NO·0.5H₂O, the Pd atom is coordinated by two S atoms from the distorted‐tetrahedral [WS₄]²⁻ anion and two P atoms from the dppb mol­ecule [dppb is 1,4‐bis(di­phenyl­phos­phino)­butane] in an approximately square‐planar configuration. A puckered seven‐membered ring is formed by the Pd atom and the dppb ligand.     

A three‐dimensional metal–organic polymer: poly[bis(μ2‐pyrimidine‐2‐thiolato‐κ4N1,S:S,N3)lead(II)]

The title compound, [Pb(C₄H₃N₂S)₂]_n, was prepared by the reaction of [Pb(OAc)₂]·3H₂O (OAc is acetate) with pyrimidine‐2‐thione in the presence of triethylamine in methanol. In the crystal structure, the Pb^II atom has an N₄S₄ coordination environment with four ligands coordinated by N‐ and S‐donor atoms. This compound shows that the pyrimidine‐2‐thiolate anion can lead to a three‐dimensional network when the coordination number of the metal ion can be higher than 6, as is the case with the Pb^II ion. This compound presents only covalent bonds, showing that despite the possibility of the hemidirected geometries of Pb^II, the eight‐coordinated ion does not allow the formation of an isolated molecular structure with pyrimidine‐2‐thiolate as the ligand.