F. Martínez

Synthesis of mono- and polynuclear perhalophenyl palladium-platinum acetylide complexes. Molecular structure of (NBu4)2[Pt2Ag2(C6F5)4(CCPh4] · 4CH2Cl2

Abstract The reaction between [Ag(CCR)]n (R = tBu, Ph) and the appropriate mononuclear palladium or platinum substrate affords mononuclear derivatives of the type [M(C6F5)(CCR)L2] (M = Pd, Pt; R = tBu, Ph; L = PPh3, dppe). Polynuclear (NBu4)2[Pt2Ag2(C6F5)4(CCPh)4] (X = F, Cl; R = Ph, tBu) complexes are obtained by reaction between (NBu4)2[Pt2(μ-X′)2(C6X5)4] (X′ = Cl, X = F; X′ = I, X = Cl) and [Ag(CCR)]n (Pt:Ag ratio 1:2). Similar heterometallic derivatives Q2[Pt2M2(C6F5)4 (CCR)4] (Q = PMePh3, NBu4; M = Ag, Cu; R = Ph, tBu) can be prepared by reaction of Q2[cis-Pt(C6F5)2(CCR)2] with AgCl or CuCl (Pt:M ratio 1:1). The structure of (NBu4)2[Pt2Ag2(C6F5)4 (CCPh)4]·4CH2Cl2 has been determined by X-ray diffraction.

Binuclear organopalladium(II) complexes with bridging biimidazolate, bibenziimidazolate or tetramethylbiimidazolate anions

Abstract Neutral and anionic pentachloro- or pentafluorophenyl palladium(II) complexes containing biimidazolate, bibenziimidazolate or 4,5-4′,5′-tetramethylbiimidazolate anions, which act as tetradentate bridging ligands, have been prepared by reacting mononuclear palladium acetylacetonate complexes with 2,2′-biimidazol, 2,2′-bibenziimidazol or, respectively 4,5-4′,5′-tetramethylbiimidazol, or by treating the thallium salts of these ligands with binuclear halide-bridged palladium(II) derivatives. The structure of the resulting complexes has been elucidated by conductance studies and IR spectroscopy.

Synthesis and reactivity of mixed pentafluorophenylpalladium(I)-platinum(I) derivatives molecular structure of ClPt(μ-dppm)2 Pd(C6F5)

Abstract XPt(μ-dppm) 2 Pd(C 6 F 5 ) (X  Cl (I), Br (II), C 6 F 5 (III) have been prepared by treating PdX(C 6 F 5 )(η 1 -dppm) 2 with Pt(COD) 2 or Pt(PPh 3 ) 4 . Substitution reactions of I yield neutral (SCN) or cationic (PPh 3 , py) derivatives. The species R 2 N + , SO 2 or RCCR (R  COOMe) insert into the PdPt bond of I to give A-frame Pd II -Pt II complexes, but reaction with SnCl 2 gives the SnCl 3 − derivative. The reactions of X-Pt(μ-dppm) 2 Pd(C 6 F 5 ) (X  Cl (I), C 6 F 5 (III)) with isonitriles RNC (R  p -Tol, Cy, t-Bu) has been studied; the nature of the products obtained depends on the starting material, the isonitrile, and the reaction conditions. The molecular structure of ClPt(μ-dppm) 2 Pd(C 6 F 5 ) has been established by a single crystal X-ray study.

Syntheses and reactivity of pentachlorophenylpalladium(I) derivatives. Molecular structure of Pd2(μ-dppm)2(C6Cl5)2

Abstract The syntheses of [XPd(μ-dppm)2Pd(C6Cl5)](X = Cl, C6Cl5 are described. Other neutral halogeno-pseudohalogeno-palladium(I) complexes [XPd(μ-dppm)2Pd(C6Cl5)] (X = Br, I, SCN or CNO) have been obtained from [ClPd(μ-dppm)2Pd(C6Cl5)] by metathetical reactions, and SnCl2 inserts into the PdCl bond to give the Pd-SnCl3 compound. The cationic derivatives [LPd(μ-dppm)2Pd(C6Cl5)]BPh4 (L = PPh3, P(OPh)3, AsPh3, SbPh3, tht) have also been prepared. SO2 or RN2+ insert into the PdPd bond of [ClPd(μ-dppm)2Pd(C6Cl5)] to give A-frame PdII complexes, but do not react with (C6Cl5)Pd(μ-dppm)2Pd(C6)Cl5. The nature of the products of the reactions of XPd(μ-dppm)2Pd(C6Cl5) with RNC (R = t-Bu, Cy, p-Tol, CNC6H4NC) depend on the isonitrile used and the reaction conditions. The molecular structure of (C6Cl5)Pd(μ-dppm)2Pd(C6Cl5) has been established by a single crystal X-ray study. The crystals are triclinic, space group P 1 , with 2 molecules of the 2 CH2ClCH2Cl solvate in a cell of dimensions a 12.986(4), b 13.213(5), c 21.254(6) A, α 90.49(3), β 89.204(25), γ 102,86(3)°, V 3554.8 A3. Of 9156 data collected on a four-circle diffractometer, 4474 observed reflections were used in the refinement (R = 0.0902). The complex has no crystallographically imposed symmetry, but overall is close to D2d. The PdPd bond length is 2.6704(21) A.

Synthesis and reactivity of bimetallic acetylide-bridged PtPt complexes. Crystal and molecular structure of [(PPh3)(C6F5)Pt(μ-CCPh)2Pt(C6F5)(PPh3)]

Abstract The binuclear double-bridged acetylide complexes [Pt(μ-CCR)(C 6 F 5 )PPh 3 )] 2 [R = Ph ( 1 ), Bu t ( 2 ), SiMe 3 ( 3 )] have been synthesized from [ trans -Pt(CCR) 2 (PPh 3 ) 2 ] and [ cis -Pt(C 6 F 5 ) 2 (THF) 2 ] (THF = tetrahydrofuran). The crystal structure of [Pt(μ-CCPh) (C 6 F 5 )(PPh 3 )] 2 ( 1 ) has been established by X-ray diffraction methods. The structure shows that two identical [(PPh 3 )(C 6 F 5 )PtCCPh] units are joined together through η 2 -bonding of MCCPh units. This indicates that the complex is formed via a rearrangement of groups between the two metal centres. Treatment of [Pt(μ-CCR)(C 6 F 5 )(PPh 3 )] 2 with L (L = PPh 3 , py = pyridine) produces simple bridge-cleavage reactions giving the mono-nuclear complexes [ trans -Pt(C 6 F 5 )(CCR)(PPh 3 )L] ( 4–9 ).

Synthesis and reactivity of acetylacetonato-Cγ complexes of MII (M Pd or Pt): X-ray crystal structure of [Pd(C6F5)(OOCPh)(bipy)]·CHCl3

Acetylacetonato-Cγ complexes of stoichiometry [M(C6X5)(acac-Cγ)(NN)] (M  Pd; X  F or Cl; NN = 1,10-phenanthroline or 2,2′-bipyridine) (MPt; XF; NN = 1,10-phenanthroline (phen), or 2,2′-bipyridine (bipy)) have been obtained by treatment of the acetylacetonato-O,O′ complexes [M(C6X5)(acac-O,O′)(tht)] (tht = tetrahydrothiophene) with the corresponding NN base in 11 molar ratio. Complexes [Pd(C6F5)(acac-Cγ)(phen)] (1) and [Pd(C6F5)(acac-Cγ)(bipy)] (2) react with organic substrates containing acidic hydrogen atoms [HR], yielding the corresponding complexes [Pd(C6F5)(R)(NN)] (R = CF3COO, CH3COO, PhCOO, PhS or P(S)Ph2). However, the reaction of 2 with HPPh2 affords the dinuclear phosphido-bridged complex [{Pd(μ-PPh2)(C6F5)(HPPh2)}2]. All complexes have been characterized by spectroscopic methods (IR and 1H, 19F and 13P{1H}NMR) and the molecular structure of [Pd(C6F5)(OOCPh)(bipy)]·CHCl3 (12) has been determined by X-ray diffraction methods.

Mononuclear gold(I) and heteronuclear gold(I)-palladium(II) bibenzimidazolate complexes with new coordination modes of the ligand

Abstract Metathetic reactions of gold(I) halide complexes and the potassium salt of 2,2′-bibenzimidazol afford binuclear bibenzimidazolate gold(I) complexes with the general formula {Au 2 L 2 }(μ-BiBzIm) L = PPh 3 , PBu n 3 , P(OMe) 3 ; L 2 = 1,1-bis(diphenylphosphine)-methane (dppm), 1,2-bis(diphenylphosphine)ethane (dppe). These complexes are Lewis bases and can be used as precursors for the synthesis of tri and tetranuclear cationic gold(I) complexes, or trinuclear gold(I) and palladium(II) complexes where the bibenzimidazolate anion is acting as bridging tetranuclear ligand. An hexanuclear gold(I)-palladium(II) complex is also described.

Synthesis and reactivity of mixed pentafluorophenyl platinum(I)−palladium(I) derivatives

Abstract XPd(μ-dppm) 2 Pt(C 6 F 5 ) (X = Cl ( I ), Br ( II )) have been prepared by reacting Pd 2 (dba) 3 ·CHCl 3 and PtX- (C 6 F 5 )(η 1 -dppm) 2 . Reaction of complex I with SnCl 2 gives the SnCl 3 − derivative, whilst ligands L (PPh 3 , P(OPh) 3 , SbPh 3 ) render the cationic complexes. The species R 2 N + , SO 2 or MeOOC)CCCOOMe insert into the PdPt bond of I to give A-frame Pd(II)- Pt(II) complexes. The reactions of CIPd(μ-dppm) 2 - Pt(C6F 5 ) with isonitriles CNR (R = p -Tol, Cy) lead to products containing either terminal or inserted isocyanide or both.

Symmetric or unsymmetric cleavage of the bridging system in [M2(μ-C6F5)2(C6F5)4]2− (M2Pt2, Pd2 or PtPd) with 2,2′-bipyridine or 1,10-phenanthroline. Molecular structure of [PPN]2[(C6F5)3Pt(μ-bpy)Pt(C6F5)3] and [NBu4][Pt(C6F5)3(phen)]☆

Abstract Binuclear M 2 (MPt, Pd) complexes with bridging NN (NNbpy) [NBu 4 ] 2 [M 2 (μ-NN)(C 6 F 5 ) 6 ], mononuclear Pt complexes with monodentate bpy or phen [NBu 4 ][Pt(C 6 F 5 ) 3 (NN)] or neutral mononuclear Pt complexes with chelating phen [Pt(C 6 F 5 ) 2 (NN)] or Pd complexes with bpy or phen [Pd(C 6 F 5 ) 2 (NN)] can be prepared starting from [NBu 4 ] 2 [M 2 (μ-C 6 F 5 ) 2 (C 6 F 5 ) 4 ] by adequate choice of solvents and reactions conditions. The crystal structures of [PPN] 2 [Pt 2 (μ-bpy)(C 6 F 5 ) 6 ] and [NBu 4 ][Pt(C 6 F 5 ) 3 (phen)] have been established by X-ray crystallography.

Synthesis and X-ray crystal structure of [Pd(C6F5)(η2-{(Ph2P)3C})(PPh3)], a mononuclear compound containing η2-tris(diphenylphosphine)methanide

Abstract The reaction between [Pd(C6F5)(acac)(PPh3)] and (Ph2P)3CH in CH2Cl2 affords [Pd(C6F5)(η2-{(Ph2P)3C})(PPh3)] (1) which can be protonated by HBF4 to yield [Pd(C6F5)(η2-{(Ph2P)3CH})(PPh3)](BF4) (2). The X-ray structure determination of complex 1 reveals a distorted square-planar environment for the metal centre with an η2-coordination of the tris(diphenylphosphino)methanide, the skeletal P3C group of this ligand is moderately distorted from a C(sp2) arrangement.