Alkynyldiphenylphosphine d8 (Pt, Rh, Ir) complexes: contrasting behavior toward cis-[Pt(C6F5)2(THF)2

The synthesis and characterization of a series of mononuclear d(8) complexes with at least two P-coordinated alkynylphosphine ligands and their reactivity toward cis-[Pt(C(6)F(5))(2)(THF)(2)] are reported. The cationic [Pt(C(6)F(5))(PPh(2)C triple-bond CPh)(3)](CF(3)SO(3)), 1, [M(COD)(PPh(2)C triple-bond CPh)(2)](ClO(4)) (M = Rh, 2, and Ir, 3), and neutral [Pt(o-C(6)H(4)E(2))(PPh(2)C triple-bond CPh)(2)] (E = O, 6, and S, 7) complexes have been prepared, and the crystal structures of 1, 2, and 7.CH(3)COCH(3) have been determined by X-ray crystallography. The course of the reactions of the mononuclear complexes 1-3, 6, and 7 with cis-[Pt(C(6)F(5))(2)(THF)(2)] is strongly influenced by the metal and the ligands. Thus, treatment of 1 with 1 equiv of cis-[Pt(C(6)F(5))(2)(THF)(2)] gives the double inserted cationic product [Pt(C(6)F(5))(S)mu-(C(Ph)=C(PPh(2))C(PPh(2))=C(Ph)(C(6)F(5)))Pt(C(6)F(5))(PPh(2)C triple-bond CPh)](CF(3)SO(3)) (S = THF, H(2)O), 8 (S = H(2)O, X-ray), which evolves in solution to the mononuclear complex [(C(6)F(5))(PPh(2)C triple-bond CPh)Pt(C(10)H(4)-1-C(6)F(5)-4-Ph-2,3-kappaPP'(PPh(2))(2))](CF(3) SO(3)), 9 (X-ray), containing a 1-pentafluorophenyl-2,3-bis(diphenylphosphine)-4-phenylnaphthalene ligand, formed by annulation of a phenyl group and loss of the Pt(C(6)F(5)) unit. However, analogous reactions using 2 or 3 as precursors afford mixtures of complexes, from which we have characterized by X-ray crystallography the alkynylphosphine oxide compound [(C(6)F(5))(2)Pt(mu-kappaO:eta(2)-PPh(2)(O)C triple-bond CPh)](2), 10, in the reaction with the iridium complex (3). Complexes 6 and 7, which contain additional potential bridging donor atoms (O, S), react with cis-[Pt(C(6)F(5))(2)(THF)(2)] in the appropriate molar ratio (1:1 or 1:2) to give homo- bi- or trinuclear [Pt(PPh(2)C triple-bond CPh)(mu-kappaE-o-C(6)H(4)E(2))(mu-kappaP:eta(2)-PPh(2)C triple-bond CPh)Pt(C(6)F(5))(2)] (E = O, 11, and S, 12) and [(Pt(mu(3)-kappa(2)EE'-o-C(6)H(4)E(2))(mu-kappaP:eta(2)-PPh(2)C triple-bond CPh)(2))(Pt(C(6)F(5))(2))(2)] (E = O, 13, and S, 14) complexes. The molecular structure of 14 has been confirmed by X-ray diffraction, and the cyclic voltammetric behavior of precursor complexes 6 and 7 and polymetallic derivatives 11-14 has been examined.     

Mixed-transition-metal acetylides: synthesis and characterization of complexes with up to six different transition metals connected by carbon-rich bridging units

The synthesis and reaction chemistry of heteromultimetallic transition-metal complexes by linking diverse metal-complex building blocks with multifunctional carbon-rich alkynyl-, benzene-, and bipyridyl-based bridging units is discussed. In context with this background, the preparation of [1-{(eta(2)-dppf)(eta(5)-C(5)H(5))RuC[triple bond]C}-3-{(tBu(2)bpy)(CO)(3)ReC[triple bond]C}-5-(PPh(2))C(6)H(3)] (10) (dppf = 1,1'-bis(diphenylphosphino)ferrocene; tBu(2)bpy = 4,4'-di-tert-butyl-2,2'-bipyridyl; Ph = phenyl) is described; this complex can react further, leading to the successful synthesis of heterometallic complexes of higher nuclearity. Heterotetrametallic transition-metal compounds were formed when 10 was reacted with [{(eta(5)-C(5)Me(5))RhCl(2)}(2)] (18), [(Et(2)S)(2)PtCl(2)] (20) or [(tht)AuC[triple bond]C-bpy] (24) (Me = methyl; Et = ethyl; tht = tetrahydrothiophene; bpy = 2,2'-bipyridyl-5-yl). Complexes [1-{(eta(2)-dppf)(eta(5)-C(5)H(5))RuC[triple bond]C}-3-{(tBu(2)bpy)(CO)(3)ReC[triple bond]C}-5-{PPh(2)RhCl(2)(eta(5)-C(5)Me(5))}C(6)H(3)] (19), [{1-[(eta(2)-dppf)(eta(5)-C(5)H(5))RuC[triple bond]C]-3-[(tBu(2)bpy)(CO)(3)ReC[triple bond]C]-5-(PPh(2))C(6)H(3)}(2)PtCl(2)] (21), and [1-{(eta(2)-dppf)(eta(5)-C(5)H(5))RuC[triple bond]C}-3-{(tBu(2)bpy)(CO)(3)ReC[triple bond]C}-5-{PPh(2)AuC[triple bond]C-bpy}C(6)H(3)] (25) were thereby obtained in good yield. After a prolonged time in solution, complex 25 undergoes a transmetallation reaction to produce [(tBu(2)bpy)(CO)(3)ReC[triple bond]C-bpy] (26). Moreover, the bipyridyl building block in 25 allowed the synthesis of Fe-Ru-Re-Au-Mo- (28) and Fe-Ru-Re-Au-Cu-Ti-based (30) assemblies on addition of [(nbd)Mo(CO)(4)] (27), (nbd = 1,5-norbornadiene), or [{[Ti](mu-sigma,pi-C[triple bond]CSiMe(3))(2)}Cu(N[triple bond]CMe)][PF(6)] (29) ([Ti] = (eta(5)-C(5)H(4)SiMe(3))(2)Ti) to 25. The identities of 5, 6, 8, 10-12, 14-16, 19, 21, 25, 26, 28, and 30 have been confirmed by elemental analysis and IR, (1)H, (13)C{(1)H}, and (31)P{(1)H} NMR spectroscopy. From selected samples ESI-TOF mass spectra were measured. The solid-state structures of 8, 12, 19 and 26 were additionally solved by single-crystal X-ray structure analysis, confirming the structural assignment made from spectroscopy.     

Acetylide-bridged organometallic oligomers via the photochemical metathesis of methyl-iron(II) complexes

The acetylido methyl iron(II) complexes, cis/trans-[Fe(dmpe)(2)(C[triple bond]CR)(CH(3))] (1) and trans-[Fe(depe)(2)(C[triple bond]CR)(CH(3))] (2) (dmpe = 1,2-dimethylphoshinoethane; depe = 1,2-diethylphosphinoethane), were synthesized by transmetalation from the corresponding alkyl halide complexes. Acetylido methyl iron(II) complexes were also formed by transmetalation from the chloride complexes, trans-[Fe(dmpe)(2)(C[triple bond]CR)(Cl)] or trans-[Fe(depe)(2)(C[triple bond]CR)(Cl)]. The structure of trans-[Fe(dmpe)(2)(C[triple bond]CC(6)H(5))(CH(3))] (1a) was determined by single-crystal X-ray diffraction. The methyl acetylido iron complexes, [Fe(dmpe)(2)(C[triple bond]CR)(CH(3))] (1), are thermally stable in the presence of acetylenes; however, under UV irradiation, methane is lost with the formation of a metal bisacetylide. Photochemical metathesis of cis- or trans-[Fe(dmpe)(2)(CH(3))(C[triple bond]CR)] (R = C(6)H(5) (1a), 4-C(6)H(4)OCH(3) (1b)) with terminal acetylenes was used to selectively synthesize unsymmetrically substituted iron(II) bisacetylide complexes of the type trans-[Fe(dmpe)(2)(C[triple bond]CR)(C[triple bond]CR')] [R = Ph, R' = Ph (6a), 4-CH(3)OC(6)H(4) (6b), (t)()Bu (6c), Si(CH(3))(3) (6d), (CH(2))(4)C[triple bond]CH (6e); R = 4-CH(3)OC(6)H(4), R' = 4-CH(3)OC(6)H(4), (6g), (t)()Bu (6h), (CH(2))(4)C[triple bond]CH (6i), adamantyl (6j)]. The structure of the unsymmetrical iron(II) bisacetylide complex trans-[Fe(dmpe)(2)(C[triple bond]CC(6)H(5))(C[triple bond]CC(6)H(4)OCH(3))] (6b) was determined by single-crystal X-ray diffraction. The photochemical metathesis of the bis-acetylene, 1,7-octadiyne, with trans-[Fe(dmpe)(2)(CH(3))(C[triple bond]CPh)] (1a), was utilized to synthesize the bridged binuclear species trans,trans-[(C(6)H(5)C[triple bond]C)Fe(dmpe)(2)(mu-C[triple bond]C(CH(2))(4)C[triple bond]C)Fe(dmpe)(2)(C[triple bond]CC(6)H(5))] (11). The trinuclear species trans,trans,trans-[(C(6)H(5)C[triple bond]C)Fe(dmpe)(2)(mu-C[triple bond]C(CH(2))(4)C[triple bond]C)Fe(dmpe)(2)(mu-C[triple bond]C(CH(2))(4)C[triple bond]C)Fe(dmpe)(2)(C[triple bond]CC(6)H(5))] (12) was synthesized by the photochemical reaction of Fe(dmpe)(2)(C[triple bond]CPh)(C[triple bond]C(CH(2))(4)C[triple bond]CH) (6e) with Fe(dmpe)(2)(CH(3))(2). Extended irradiation of the bisacetylide complexes with phenylacetylene resulted in insertion of the terminal alkyne into one of the metal acetylide bonds to give acetylide butenyne complexes. The structure of the acetylide butenyne complex, trans-[Fe(dmpe)(2)(C[triple bond]CC(6)H(4)OCH(3))(eta(1)-C(C(6)H(5))=CH(C[triple bond]CC(6)H(4)OCH(3)))] (9a) was determined by single-crystal X-ray diffraction.     

Synthesis,molecular structure,and C-C coupling reactions of carbeneruthenium(II) complexes with C5H5Ru(=CRR') and C5Me5Ru(=CRR') as molecular units

The ethene derivatives [(eta(5)-C(5)R(5))RuX(C(2)H(4))(PPh(3))] with R=H and Me, which have been prepared from the eta(3)-allylic compounds [(eta(5)-C(5)R(5))Ru(eta(3)-2-MeC(3)H(4))(PPh(3))] (1, 2) and acids HX under an ethene atmosphere, are excellent starting materials for the synthesis of a series of new halfsandwich-type ruthenium(II) complexes. The olefinic ligand is replaced not only by CO and pyridine, but also by internal and terminal alkynes to give (for X=Cl) alkyne, vinylidene, and allene compounds of the general composition [(eta(5)-C(5)R(5))RuCl(L)(PPh(3))] with L=C(2)(CO(2)Me)(2), Me(3)SiC(2)CO(2)Et, C=CHCO(2)R, and C(3)H(4). The allenylidene complex [(eta(5)-C(5)H(5))RuCl(=C=C=CPh(2))(PPh(3))] is directly accessible from 1 (R=H) in two steps with the propargylic alcohol HC triple bond CC(OH)Ph(2) as the precursor. The reactions of the ethene derivatives [(eta(5)-C(5)H(5))RuX(C(2)H(4))(PPh(3))] (X=Cl, CF(3)CO(2)) with diazo compounds RR'CN(2) yield the corresponding carbene complexes [(eta(5)-C(5)R(5))RuX(=CRR')(PPh(3))], while with ethyl diazoacetate (for X=Cl) the diethyl maleate compound [(eta(5)-C(5)H(5))RuCl[eta(2)-Z-C(2)H(2)(CO(2)Et)(2)](PPh(3))] is obtained. Halfsandwich-type ruthenium(II) complexes [(eta(5)-C(5)R(5))RuCl(=CHR')(PPh(3))] with secondary carbenes as ligands, as well as cationic species [(eta(5)-C(5)H(5))Ru(=CPh(2))(L)(PPh(3))]X with L=CO and CNtBu and X=AlCl(4) and PF(6), have also been prepared. The neutral compounds [(eta(5)-C(5)H(5))RuCl(=CRR')(PPh(3))] react with phenyllithium, methyllithium, and the vinyl Grignard reagent CH(2)=CHMgBr by displacement of the chloride and subsequent C-C coupling to generate halfsandwich-type ruthenium(II) complexes with eta(3)-benzyl, eta(3)-allyl, and substituted olefins as ligands. Protolytic cleavage of the metal-allylic bond in [(eta(5)-C(5)H(5))Ru(eta(3)-CH(2)CHCR(2))(PPh(3))] with acetic acid affords the corresponding olefins R(2)C=CHCH(3). The by-product of this process is the acetato derivative [(eta(5)-C(5)H(5))Ru(kappa(2)-O(2)CCH(3))(PPh(3))], which can be reconverted to the carbene complexes [(eta(5)-C(5)H(5))RuCl(=CR(2))(PPh(3))] in a one-pot reaction with R(2)CN(2) and Et(3)NHCl.     

C-H and P-C(Ph) activation competitive processes caused by interaction with the solvate [cis-Pt(C6F5)2(thf)2

The study of the reaction between the ethylene [Pt(eta-H2C = CH2)(PPh3)2] or alkyne [Pt(eta2-HC [triple bond] CR)(PPh3)2] (R = SiMe3 1, Bu(t) 2) complexes with [cis-Pt(C6F5)2(thf)2] (thf = tetrahydrofuran) has enabled us to observe the existence of competitive processes between the activation of a P-C(Ph) bond on the PPh3 ligand, to give the binuclear derivative [cis-(C6F5)2Pt(mu-Ph)(mu-PPh2)Pt(PPh3)] 3, and the activation of a C-H bond of the unsaturated group, to give the corresponding (mu-hydride)(mu-vinyl) [cis, cis-(PPh3)2Pt(mu-H)(mu-1kappaC(alpha):eta2-CH = CH2)Pt(C6F5)2] 4 or (mu-hydride)(mu-alkynyl) [cis,cis-(PPh3)2Pt(mu-H)(mu-1kappaC(alpha):eta2-C [triple bond]CR)Pt(C6F5)2] (R = SiMe3 5, Bu(t) 6) compounds, respectively. The monitoring of these reactions by NMR spectroscopy has allowed us to detect several intermediates, and to propose a mechanism for the C-H bond activation. In addition, the structures of the (muo-hydride)(mu-alkynyl) complex 5 and the unprecedented (mu-hydride)(mu-vinyl) derivative 4 have been obtained by X-ray crystallographic analyses.     

One-dimensional phosphinite platinum chains based on hydrogen bonding interactions and phosphinite tetranuclear platinum(II)-thallium(I) complexes

The mononuclear pentafluorophenyl platinum complex containing the chelated diphenylphosphinous acid/diphenylphosphinite system [Pt(C(6)F(5)){(PPh(2)O)(2)H}(PPh(2)OH)] 1 has been prepared and characterised. 1 and the related alkynyl complex [Pt(C[triple bond, length as m-dash]CBu(t)){(PPh(2)O)(2)H}(PPh(2)OH)] 2 form infinite one-dimensional chains in the solid state based on intermolecular O-H[dot dot dot]O hydrogen bonding interactions. Deprotonation reactions of [PtL{(PPh(2)O)(2)H}(PPh(2)OH)] (L = C(6)F(5), C[triple bond, length as m-dash]CBu(t), C[triple bond, length as m-dash]CPh 3) with [Tl(acac)] yields tetranuclear Pt(2)Tl(2) complexes [PtL{(PPh(2)O)(2)H}(PPh(2)O)Tl](2) (L = C(6)F(5) 4, C[triple bond, length as m-dash]CBu(t), C[triple bond, length as m-dash]CPh ). The structure of the tert-butylalkynyl derivative , established by X-ray diffraction, shows two anionic discrete units [Pt(C[triple bond, length as m-dash]CBu(t)){(PPh(2)O)(2)H}(PPh(2)O)](-) joined by two Tl(i) centres via Tl-O and Pt-Tl bonds. Despite the existence of Pt-Tl interactions, they do not show luminescence.     

Formation of a cyclobutylidene ring: intramolecular [2 + 2] cycloaddition of allyl and vinylidene C=C bonds under mild conditions

Intramolecular [2 + 2] cycloaddition of two C=C bonds in vinylidene complexes [Ru(eta5-C9H7){=C=C(R)H}(PPh3){kappa1-(P)-PPh2(C3H5)][BF4] affords cyclobutylidene complexes [Ru(eta5-C9H7){kappa2-(P,C)-(=CC(R)HCH2CHCH2PPh2)}(PPh3)][BF4], which can be also obtained by reaction of terminal alkynes with [Ru(eta5-C9H7)(PPh3){kappa3-(P,C,C)-PPh2(C3H5)}][PF6]. The reaction proceeds under mild conditions via vinylidene complexes, and the activation parameters were determined by kinetic studies.     

ortho-Metallated complexes of platinum(II) and diplatinum(I) containing the carbanions (2-diphenylphosphino)phenyl and (2-diphenylphosphino)-n-tolyl (n = 5, 6)

When the ortho-metallated complexes cis-[Pt(kappa(2)-C6H3-5-R-2-PPh2)2] (R = H 1, Me 2) are either heated in toluene or treated with CO at room temperature, one of the four-membered chelate rings is opened irreversibly to give dinuclear isomers [Pt2(kappa(2)-C6H3-5-R-2-PPh2)2(mu-C6H3-5-R-2-PPh2)2] (R = H 10, Me 11). A single-crystal X-ray diffraction study shows the Pt...Pt separation in 10 to be 3.3875(4) A. By-products of the reactions of 1 and 2 with CO are polymeric isomers (R = H 13, Me 14) in which one of the P-C ligands is believed to bridge adjacent platinum atoms intermolecularly. In contrast to the behaviour of 1 and 2, when cis-[Pt(kappa(2)-C6H3-6-Me-2-PPh2)2] (cis-3) is heated in toluene, the main product is trans-3, and reaction of cis-3 with CO gives a carbonyl complex [Pt(CO)(kappa(1)-C-C6H3-6-Me-2-PPh2)(2-C6H3-6-Me-2-PPh2)] 15, in which one of the carbanions is coordinated only through the carbon. Formation of a dimer analogous to 10 or 11 is sterically hindered by the 6-methyl substituent. Comproportionation of 1 or 2 with [Pt(PPh3)2L] (L = PPh3, C2H4) gives diplatinum(I) complexes [Pt2(mu-C6H3-5-R-2-PPh2)2(PPh3)2] (R = H 16, Me 17). An X-ray diffraction study shows that 17 contains a pair of planar-coordinated metal atoms separated by 2.61762(16) A. There is no evidence for the formation of an analogue containing mu-C6H3-6-Me-2-PPh2. The axial PPh3 ligands of 16 are readily replaced by ButNC giving [Pt2(mu-2-C6H4PPh2)2(CNBut)2] 18, which is protonated by HBF4 to form a mu-hydridodiplatinum(II) salt [Pt2(mu-H)(mu-2-C6H4PPh2)2(CNBut)2]BF4 [21]BF4. The J(PtPt) values in [21]BF4 and 18, 2700 Hz and 4421 Hz, respectively, reflect the weakening of the Pt-Pt interaction caused by protonation. Similarly, 16 and 17 react with the electrophiles iodine and strong acids to give salts of general formula [Pt2(mu-Z)(mu-C6H3-5-R-2-PPh2)2(PPh3)2]Y (Y = Z = I, R = H 19+, Me 20+; Z = H, Y = BF4, PF6, OTf, R = H 22+; Z = H, Y = PF6, R = Me 23+). A single-crystal X-ray diffraction study of [23]PF6 shows that the cation has an approximately A-frame geometry, with a Pt-Pt separation of 2.7888(3) A and a Pt-H bond length of 1.62(1) A, and that the 5-methyl substituents have undergone partial exchange with the 4-hydrogen atoms of the PPh2 groups of the bridging carbanion. The latter observation indicates that the added proton of [23]+ undergoes a reversible reductive elimination-oxidative addition sequence with the Pt-C(aryl) bonds.     

Aluminacyclopropene: syntheses, characterization, and reactivity toward terminal alkynes

Reactions of LAl with ethyne, mono- and disubstituted alkynes, and diyne to aluminacyclopropene LAl[eta2-C2(R1)(R2)] ((L = HC[(CMe)(NAr)]2, Ar = 2,6-iPr2C6H3); R1 = R2 = H, (1); R1 = H, R2 = Ph, (2); R1 = R2 = Me, (3); R1 = SiMe3, R2 = C[triple bond]CSiMe3, (4)) are reported. Compounds 1 and 2 were obtained in equimolar quantities of the starting materials at low temperature. The amount of C2H2 was controlled by removing an excess of C2H2 in the range from -78 to -50 degrees C. Compound 4 can be alternatively prepared by the substitution reaction of LAl[eta2-C2(SiMe3)2] with Me3SiC[triple bond]CC[triple bond]CSiMe3 or by the reductive coupling reaction of LAlI2 with potassium in the presence of Me3SiC[triple bond]CC[triple bond]CSiMe3. The reaction of LAl with excess C2H2 and PhC[triple bond]CH (<1:2) afforded the respective alkenylalkynylaluminum compounds LAl(CH=CH2)(C[triple bond]CH) (5) and LAl(CH=CHPh)(C[triple bond]CPh) (6). The reaction of LAl(eta2-C2Ph2) with C2H2 and PhC[triple bond]CH yielded LAl(CPh=CHPh)(C[triple bond]CH) (7) and LAl(CPh=CHPh)(C[triple bond]CPh) (8), respectively. Rationally, the formation of 5 (or 6) may proceed through the corresponding precursor 1 (or 2). The theoretical studies based on DFT calculations show that an interaction between the Al(I) center and the C[triple bond]C unit needs almost no activation energy. Within the AlC2 ring the computational Al-C bond order of ca. 1 suggests an Al-C sigma bond and therefore less pi electron delocalization over the AlC2 ring. The computed Al-eta2-C2 bond dissociation energies (155-82.6 kJ/mol) indicate a remarkable reactivity of aluminacyclopropene species. Finally, the 1H NMR spectroscopy monitored reaction of LAl(eta2-C2Ph2) and PhC[triple bond]CH in toluene-d8 may reveal an acetylenic hydrogen migration process.     

Synthetic,structural, electrochemical,and theoretical studies of heterometallic aggregates with a [Pt(2)(mu-S)(2)M] core (M = Hg,Au)

Novel electroactive multimetallic compounds based on the [Pt(2)(mu(2)-S)(2)M] core, viz. [Pt(2)(PPh(3))(4)(mu(3)-S)(2)HgFc]PF(6) (1) [Fc = (eta(5)-C(5)H(4))Fe(eta(5)-C(5)H(5))] and [Pt(2)(PPh(3))(4)(mu(3)-S)(2)Hg(2)Fc'](PF(6))(2) (2) [Fc' = Fe(eta(5)-C(5)H(4))(2)], have been synthesized under the guide of electrospray mass spectrometry. The electrochemistry of these ferrocene funtionalized compounds together with the reported [Pt(2)(PPh(3))(4)(mu(3)-S)(2)HgPPh(3)](PF(6))(2) (3), [Pt(2)(PPh(3))(4)(mu(2)-S)(mu(3)-S)HgPh]PF(6) (4), and [Pt(2)(PPh(3))(4)(mu(2)-S)(mu(3)-S)AuPPh(3)]PF(6) (5) have been investigated using cyclic voltammetry and DFT calculations. These results point to a prominent ligand-based oxidation.     

Sigma-organyl complexes of ruthenium and osmium supported by a mixed-donor ligand

A series of vinyl, aryl, acetylide and silyl complexes [Ru(R)(kappa2-MI)(CO)(PPh3)2] (R = CH=CH2, CH=CHPh, CH=CHC6H4CH3-4, CH=CH(t)Bu, CH=2OH, C(C triple bond CPh)=CHPh, C6H5, C triple bond CPh, SiMe2OEt; MI = 1-methylimidazole-2-thiolate) were prepared from either [Ru(R)Cl(CO)(PPh3)2] or [Ru(R)Cl(CO)(BTD)(PPh3)2](BTD = 2,1,3-benzothiadiazole) by reaction with the nitrogen-sulfur mixed-donor ligand, 1-methyl-2-mercaptoimidazole (HMI), in the presence of base. In the same manner, [Os(CH=CHPh)(kappa2-MI)(CO)(PPh3)2] was prepared from [Os(CH=CHPh)(CO)Cl(BTD)(PPh3)2]. The in situ hydroruthenation of 1-ethynylcyclohexan-1-ol by [RuH(CO)Cl(BTD)(PPh3)2] and subsequent addition of the HMI ligand and excess sodium methoxide yielded the dehydrated 1,3-dienyl complex [Ru(CH=CHC6H9)(kappa2-MI)(CO)(PPh3)2]. Dehydration of the complex [Ru(CH=CHCPh2OH)(kappa2-MI)(CO)(PPh3)2] with HBF4 yielded the vinyl carbene [Ru(=CHCH=CPh2)(kappa2-MI)(CO)(PPh3)2]BF4. The hydride complexes [MH(kappa2-MI)(CO)(PPh3)2](M = Ru, Os) were obtained from the reaction of HMI and KOH with [RuHCl(CO)(PPh3)3] and [OsHCl(CO)(BTD)(PPh3)2], respectively. Reaction of [Ru(CH=CHC6H4CH3-4)(kappa2-MI)(CO)(PPh3)2] with excess HC triple bond CPh leads to isolation of the acetylide complex [Ru(C triple bond CPh)(kappa2-MI)(CO)(PPh3)2], which is also accessible by direct reaction of [Ru(C triple bond CPh)Cl(CO)(BTD)(PPh3)2] with 1-methyl-2-mercaptoimidazole and NaOMe. The thiocarbonyl complex [Ru(CPh = CHPh)Cl(CS)(PPh3)2] reacted with HMI and NaOMe without migration to yield [Ru(CPh= CHPh)(kappa2-MI)(CS)(PPh3)2], while treatment of [Ru(CH=CHPh)Cl(CO)2(PPh3)2] with HMI yielded the monodentate acyl product [Ru{eta(1)-C(=O)CH=CHPh}(kappa2-MI)(CO)(PPh3)2]. The single-crystal X-ray structures of five complexes bearing vinyl, aryl, acetylide and dienyl functionality are reported.     

Behavior of neutral phosphido derivatives of platinum and palladium toward silver centers

The reaction of the neutral binuclear complexes [(R(F))(2)Pt(μ-PPh(2))(2)M(phen)] (phen = 1,10-phenanthroline, R(F) = C(6)F(5); M = Pt, 1; M = Pd, 2) with AgClO(4) or [Ag(OClO(3))(PPh(3))] affords the trinuclear complexes [AgPt(2)(μ-PPh(2))(2)(R(F))(2)(phen)(OClO(3))] (7a) or [AgPtM(μ-PPh(2))(2)(R(F))(2)(phen)(PPh(3))][ClO(4)] (M = Pt, 8; M = Pd, 9), which display an "open-book" type structure and two (7a) or one (8, 9) Pt-Ag bonds. The neutral diphosphine complexes [(R(F))(2)Pt(μ-PPh(2))(2)M(P-P)] (P-P = 1,2-bis(diphenylphosphino)methane, dppm, M = Pt, 3; M = Pd, 4; P-P = 1,2-bis(diphenylphosphino)ethane, dppe, M = Pt, 5; M = Pd, 6) react with AgClO(4) or [Ag(OClO(3))(PPh(3))], and the nature of the resulting complexes is dependent on both M and the diphosphine. The dppm Pt-Pt complex 3 reacts with [Ag(OClO(3))(PPh(3))], affording a silver adduct 10 in which the Ag atom interacts with the Pt atoms, while the dppm Pt-Pd complex 4 reacts with [Ag(OClO(3))(PPh(3))], forming a 1:1 mixture of [AgPdPt(μ-PPh(2))(2)(R(F))(2)(OClO(3))(dppm)] (11), in which the silver atom is connected to the Pt-Pd moiety through Pd-(μ-PPh(2))-Ag and Ag-P(k(1)-dppm) interactions, and [AgPdPt(μ-PPh(2))(2)(R(F))(2)(OClO(3))(PPh(3))(2)][ClO(4)] (12). The reaction of complex 4 with AgClO(4) gives the trinuclear derivative 11 as the only product. Complex 11 shows a dynamic process in solution in which the silver atom interacts alternatively with both Pd-μPPh(2) bonds. When P-P is dppe, both complexes 5 and 6 react with AgClO(4) or [Ag(OClO(3))(PPh(3))], forming the saturated complexes [(PPh(2)C(6)F(5))(R(F))Pt(μ-PPh(2))(μ-OH)M(dppe)][ClO(4)] (M = Pt, 13; Pd, 14), which are the result of an oxidation followed by a PPh(2)/C(6)F(5) reductive coupling. Finally, the oxidation of trinuclear derivatives [(R(F))(2)Pt(II)(μ-PPh(2))(2)Pt(II)(μ-PPh(2))(2)Pt(II)L(2)] (L(2) = phen, 15; L = PPh(3), 16) by AgClO(4) results in the formation of the unsaturated 46 VEC complexes [(R(F))(2)Pt(III)(μ-PPh(2))(2)Pt(III)(μ-PPh(2))(2)Pt(II)L(2)][ClO(4)](2) (17 and 18, respectively) which display Pt(III)-Pt(III) bonds.     

Synthesis, dynamic behavior, and reactivity of new unsaturated heterotrinuclear 46 valence electron complexes

The reaction of [NBu(4)](2)[(C(6)F(5))(2)Pt(μ-PPh(2))(2)Pd(μ-PPh(2))(2)Pt(C(6)F(5))(2)] (1a) with [AgPPh(3)](+) results in the oxidation of two bridging diphenylphosphanides to give the 46e species [(PPh(3))(C(6)F(5))(2)Pt(2)(μ-P(2)Ph(2))Pd(μ-PPh(2))(μ-Ph(2)P(4)-P(3)Ph(2))Pt(1)(C(6)F(5))(2)] (3). Complex 3 displays two tetracoordinated terminal platinum centers and a central Pd atom that is bonded to three P atoms and that completes its coordination sphere by a rather long (3.237 ?) dative Pt(2) → Pd bond. Complex 3 is also obtained when [(R(F))(2)Pt(μ-PPh(2))Pd(μ-PPh(2))(μ-Ph(2)P-PPh(2))Pt(R(F))(2)] (2) is reacted with PPh(3). Analogously, the addition of PPh(2)Et, CO or pyridine to 2 affords the 46e complexes of general formula [(L)(C(6)F(5))(2)Pt(2)(μ-P(2)Ph(2))Pd(μ-PPh(2))(μ-Ph(2)P(4)-P(3)Ph(2))Pt(1)(C(6)F(5))(2)] (L = PPh(2)Et, 4; L = CO, 6; L = pyridine, 7). The geometry around Pt(2) is determined by the bulkiness of L bonded to Pt. Thus, in complexes 3 (L = PPh(3)) and 4 (L = PPh(2)Et), the ligand L occupies the trans position with respect to μ-P(2), and in 6 (L = CO), the ligand L occupies the cis position with respect to μ-P(2). Interestingly, for 7 (L = py), both isomers 7-trans and 7-cis, could be isolated. Although 4 did not react with an excess of PPh(2)Et, the reaction with the less sterically demanding CH(3)CN ligand resulted in the opening of the Pt(2)-P(2)-Pd cycle with formation of the saturated 48e species [(PPh(2)Et)(C(6)F(5))(2)Pt(μ-PPh(2))Pd(MeCN)(μ-PPh(2))(μ-Ph(2)P-PPh(2))Pt(C(6)F(5))(2)] (8). The saturated 48e complex [(CO)(C(6)F(5))(2)Pt(μ-PPh(2))Pd(MeCN)(μ-PPh(2))(μ-Ph(2)P-PPh(2))Pt(C(6)F(5))(2)] (9) was obtained by acetonitrile addition to 6. Beside the hindered rotation of the pentafluorophenyl groups and a flip-flop motion of the Pd-P-Pt(1)-P-P ring observed at low T, a rotation about the Pt(2)-P(2) bond and a P-C oxidative addition/reductive elimination process occur for 3 and 4 at room temperature. A "through-space" (19)F-(31)P spin-spin coupling between an ortho-F and the P(4) is observed for complexes 3 and 4, having the C(6)F(5) groups bonded to Pt(2) in mutually trans position. The XRD structures of complexes 3, 6, 7-trans, 7-cis, 8, and 9 are described.     

Formation of diphenylphosphanylbutadienyl complexes by insertion of two P-coordinated alkynylphosphanes into a PtbondC6F5 bond: detection of intermediate and reaction products

The reactions between cis-[M(C(6)F(5))(2)(PPh(2)CtriplebondCR)(2)] (M=Pt, Pd; R=Ph, tBu, Tol 2, 3) or cis-[Pt(C(6)F(5))(2)(PPh(2)CtriplebondCR)(PPh(2)CtriplebondCtBu)] (R=Ph 4, Tol 5) and cis-[Pt(C(6)F(5))(2)(thf)(2)] 1 have been investigated. Whereas [M](PPh(2)CtriplebondCtBu)(2) ([M]=cis-M(C(6)F(5))(2)) is inert towards 1, the analogous reactions starting from [M](PPh(2)CtriplebondCR)(2) or [Pt](PPh(2)CtriplebondCR)(PPh(2)CtriplebondCtBu) (R=Ph, Tol) afford unusual binuclear species [Pt(C(6)F(5))(S)mu-[C(R')dbondC(PPh(2))C(PPh(2))doublebondC(R)(C(6)F(5))]M(C(6)F(5))(2)] (R=R'=Ph, Tol, M=Pt 6 a,c, M=Pd 7 a,c; M=Pt, R'=tBu, R=Ph 8, Tol 9) containing a bis(diphenylphosphanyl)butadienyl bridging ligand formed by an unprecedented sequential insertion reaction of two P-coordinated PPh(2)CtriplebondCR ligands into a PtbondC(6)F(5) bond. Although in solution the presence of coordinated solvent S (S=(thf)(x)(H(2)O)(y)) in 6, 7 is suggested by NMR spectroscopy, X-ray diffraction analyses of different crystals of the mixed complex [Pt(C(6)F(5))mu-[C(tBu)doublebondC(PPh(2))C(PPh(2))doublebondC(Tol)(C(6)F(5))]Pt(C(6)F(5))(2)] 9 unequivocally establish that in the solid state the steric crowding of the new diphenylbutadienyl ligand formed stabilizes an unusual coordinatively unsaturated T-shaped 3-coordinated platinum(II) center. Structure determinations of the mononuclear precursors cis-[Pt(C(6)F(5))(2)(PPh(2)CtriplebondCR)(2)] (R=Ph, tBu, Tol) have been carried out to evaluate the factors affecting the insertion processes. The reactions of the platinum complexes 6 towards neutral ligands (L=CO, py, PPh(2)H, CNtBu) in a 1:1 molar ratio afford related diplatinum derivatives 10-13, whereas treatment with CNtBu (1:2 molar ratio) or 2,2'-bipy (1:1 molar ratio) results in the opening of the chelating ring to give cis,cis-[Pt(C(6)F(5))(L)(2)mu-[1-kappaC(1):2-kappaPP'-C(R)doublebondC(PPh(2))C(PPh(2))doublebondC(R)(C(6)F(5))]Pt(C(6)F(5))(2)] (14, 15). The unsaturated or solvento complexes are unstable in solution evolving firstly, through an unexpected formal 4-1 R (Ph, Tol) migration, to the intermediate diphosphanylbutadienyl isomer derivatives [Pt(C(6)F(5))(S)mu-[C(C(6)F(5))doublebondC(PPh(2))C(PPh(2))doublebondC(R)(2)]M(C(6)F(5))(2)] (16, 18) (X-ray, R=Ph, M=Pt) and, finally, to 1-pentafluorophenyl-2,3-bis(diphenylphosphanyl)naphthalene mononuclear complexes (17, 19) by annulation of a phenyl or tolyl group.     

Transition metal vinylidene complexes as supramolecular building blocks: nucleobase-mediated self-assembly of crystals with hexagonal symmetry

Reaction of the ruthenium half sandwich compound RuCl(eta(5)-C(5)H(5))(PPh(3))(2) with the uracil (Ur) substituted alkyne HC[triple bond, length as m-dash]CUr in the presence of halide scavengers NH(4)X (X = PF(6), BF(4), OTf) results in the formation of the vinylidene complexes [Ru([double bond, length as m-dash]C[double bond, length as m-dash]CHUr)(eta(5)-C(5)H(5))(PPh(3))(2)][X] which crystallize in the hexagonal space group P6(3)/m. The hexagonal symmetry inherent to the system is due to the formation of a hydrogen bonded array mediated by the two sets of donor-acceptor units on the uracil, resulting in the formation of a cyclic "rosette" containing six ruthenium cations. In solution the (1)H and (31)P{(1)H} NMR spectra of the vinylidene complexes are both concentration and temperature dependent, in accord with the presence of monomer-dimer equilibria in which the rate of rotation of the vinylidene group is fast on the NMR timescale in the monomeric species, but slow in the dimers. The isoelectronic molybdenum-containing vinylidene complex [Mo(eta(7)-C(7)H(7))(dppe)([double bond, length as m-dash]C[double bond, length as m-dash]CHUr)][BF(4)] (dppe = 1,2-bis(diphenylphosphino)ethane) has also been prepared, but forms symmetric dimers in the solid state.     

Organometallic building blocks with amino-substituted cyclopentadienyl and boratabenzene ligands for the synthesis of heterometallic complexes and clusters

A comparative study of the reactivity of isolobal rhenium and molybdenum carbonylmetallates containing a borole, in [Re(eta5-C4H4BPh)(CO)3]- (2), a boratanaphthalene, in [Mo(eta5-2,4-MeC9H6BMe)(CO)3]- (4a) and [Mo(eta5-2,4-MeC9H6BNi-Pr2)(CO)3]- (4b), a boratabenzene, in [Mo(eta5-3,5-Me2C5H3BNi-Pr2)(CO)3]- (6) or a dimethylaminocyclopentadienyl ligand, in [Mo(eta5-C5H4NMe2)(CO)3]- (7), toward palladium(II), gold(I), mercury(II) and platinum(II) complexes has allowed an evaluation of the role of these pi-bonded ligands on the structures and unprecedented coordination modes observed in the resulting metal-metal bonded, heterometallic complexes. The new metallate 6 was reacted with [AuCl(PPh3)], and with 1 or 2 equiv. HgCl2, which afforded the new heterodinuclear complexes [Au{Mo(eta5-3,5-Me2C5H3BNi-Pr2)(CO)3}(PPh3)] (Mo-Au) (10) and [Hg{Mo(eta5-3,5-Me2C5H3BNi-Pr2)(CO)3}Cl] (Hg-Mo) (11) and the heterometallic chain complex [Hg{Mo(eta5-3,5-Me2C5H3BNi-Pr2)(CO)3}2] (Mo-Hg-Mo) (12), respectively. Reactions of the new metallate 7 with HgCl2, trans-[PtCl2(CNt-Bu)2] and trans-[PtCl2(NCPh)2] yielded the heterodinuclear complex [Hg{Mo(eta5-C5H4NMe2)(CO)3}Cl] (Mo-Hg) (15), the heterotrinuclear chain complexes trans-[Pt{Mo(eta5-C5H4NMe2)(CO)3}2(CNt-Bu)2] (Mo-Pt-Mo) (16) and trans-[Pt{Mo(eta5-C5H4NMe2)(CO)3}2(NCPh)2] (Mo-Pt-Mo) (17), the mononuclear complex [Mo(eta5-C5H4NMe2)(CO)3Cl] (18), the lozenge-type cluster [Mo2Pt2(eta5-C5H4NMe2)2(CO)8] (19) and the heterodinuclear complex [[upper bond 1 start]Pt{Mo(eta5-C5H4N[upper bond 1 end]Me2)(CO)3}(NCPh)Cl](Mo-Pt) (20), respectively. The complexes 11, 16, 17.2THF, 18 and 20 have been structurally characterized by X-ray diffraction and 20 differs from all other compounds in that the dimethylaminocyclopentadienyl ligand forms a bridge between the metals.     

Formation and reactions of metal-metal bonded heterobimetallic (C5H4PR2)-bridged (Zr-Ir) and (Zr-Rh) complexes: evidence for the participation of metal hydride intermediates

Treatment of the complexes [(C(5)H(4)PR(2))(2)Zr(CH(3))(2)](b: R = isopropyl; c: R = cyclohexyl) with the reagent HIr(CO)(PPh(3))(3) (2b) yield the heterobimetallic complexes [mu-C(5)H(4)PR(2))(2)(H(3)C-Zr-Ir(CO)(PPh(3)))] (4b, 4c) with evolution of methane. The reaction of the -PPh(2) substituted analogue with initially yields an intermediate [(H(3)C)(2)Zr(mu-C(5)H(4)PPh(2))(2)Ir(H)(CO)(PPh(3))] 5a, that still contains both methyl groups at zirconium and does not contain a metal-metal bond. At room temperature, the intermediate reacts further with methane formation to eventually yield the (Zr-Ir) complex 4a. The corresponding [mu-C(5)H(4)PR(2))(2)(H(3)C-Zr-Rh(CO)(PPh(3)))] complexes 3a (R = Ph) and 3b (R = isopropyl) react cleanly with isopropyl alcohol to liberate methane and yield the corresponding [mu-C(5)H(4)PR(2))(2)(Me(2)CHO-Zr-Rh(CO)(PPh(3)))] products (7a, 7b). Carefully monitoring the reaction of with Me(2)CHOH by NMR revealed that the Zr-Rh functionality is attacked first to give the intermediate [Me(Me(2)CHO)Zr([micro sign]-C(5)H(4)PR(2))(2)Rh(H)(CO)(PPh(3))] (6b). This intermediate then reacts further to cleave off methane and re-form the (Zr-Rh) metal-metal bond to yield the product 7b. The tetrametallic mu-oxo-(Zr-Rh) metallocene derivate 11a was obtained starting from the (Zr-Rh) complex 3a and it was characterized by X-ray diffraction. It may be that this reaction is also initiated by H-OH addition to the [Zr-Rh] metal-metal bond.     

Subtle reactivity patterns of non-heteroatom-substituted manganese alkynyl carbene complexes in the presence of phosphorus probes

The non-heteroatom-substituted manganese alkynyl carbene complexes (eta5-MeC5H4)(CO)2Mn=C(R)C[triple bond]CR'(3; 3a: R = R'= Ph, 3b: R = Ph, R'= Tol, 3c: R = Tol, R'= Ph) have been synthesised in high yields upon treatment of the corresponding carbyne complexes [eta5-MeC5H4)(CO)2Mn[triple bond]CR][BPh4]([2][BPh4]) with the appropriate alkynyllithium reagents LiC[triple bond]CR' (R'= Ph, Tol). The use of tetraphenylborate as counter anion associated with the cationic carbyne complexes has been decisive. The X-ray structures of (eta5-MeC5H4)(CO)2Mn=C(Tol)C[triple bond]CPh (3c), and its precursor [(eta5-MeC5H4)(CO)2Mn=CTol][BPh4]([2b](BPh4]) are reported. The reactivity of complexes toward phosphines has been investigated. In the presence of PPh3, complexes act as a Michael acceptor to afford the zwitterionic sigma-allenylphosphonium complexes (eta5-MeC5H4)(CO)2MnC(R)=C=C(PPh3)R' (5) resulting from nucleophilic attack by the phosphine on the remote alkynyl carbon atom. Complexes 5 exhibit a dynamic process in solution, which has been rationalized in terms of a fast [NMR time-scale] rotation of the allene substituents around the allene axis; metrical features within the X-ray structure of (eta5-MeC5H4)(CO)2MnC(Ph)=C=C(PPh3)Tol (5b) support the proposal. In the presence of PMe3, complexes undergo a nucleophilic attack on the carbene carbon atom to give zwitterionic sigma-propargylphosphonium complexes (eta5-MeC5H4)(CO)2MnC(R)(PMe3)C[triple bond]CR' (6). Complexes 6 readily isomerise in solution to give the sigma-allenylphosphonium complexes (eta5-MeC5H4)(CO)2MnC(R')=C=C(PMe3)R (7) through a 1,3 shift of the [(eta5-MeC5H4)(CO)2Mn] fragment. The nucleophilic attack of PPh2Me on 3 is not selective and leads to a mixture of the sigma-propargylphosphonium complexes (eta5-MeC5H4)(CO)2MnC(R)(PPh(2)Me)C[triple bond]CR' (9) and the sigma-allenylphosphonium complexes (eta5-MeC5H4)(CO)2MnC(R)=C=C(PPh(2)Me)R' (10). Like complexes 6, complexes 9 readily isomerize to give the sigma-allenylphosphonium complexes (eta5-MeC5H4)(CO)2MnC(R')=C=C(PPh2Me)R'). Upon gentle heating, complexes 7, and mixtures of 10 and 10' cyclise to give the sigma-dihydrophospholium complexes (eta5-MeC5H4)(CO)2MnC=C(R')PMe2CH2CH(R)(8), and mixtures of complexes (eta5-MeC5H4)(CO)2MnC=C(Ph)PPh2CH2CH(Tol)(11) and (eta5-MeC5H4)(CO)2MnC=C(Tol)PMe2CH2CH(Ph)(11'), respectively. The reactions of complexes 3 with secondary phosphines HPR(1)(2)(R1= Ph, Cy) give a mixture of the eta2-allene complexes (eta5-MeC5H4)(CO)2Mn[eta2-{R(1)(2)PC(R)=C=C(R')H}](12), and the regioisomeric eta4-vinylketene complexes [eta5-MeC5H4)(CO)Mn[eta4-{R(1)(2)PC(R)=CHC(R')=C=O}](13) and (eta5-MeC5H4)(CO)Mn[eta4-{R(1)(2)PC(R')=CHC(R)=C=O}](13'). The solid-state structure of (eta5-MeC5H4)(CO)2Mn[eta2-{Ph2PC(Ph)=C=C(Tol)H}](12b) and (eta5-MeC5H4)(CO)Mn[eta4-{Cy2PC(Ph)=CHC(Ph)=C=O}](13d) are reported. Finally, a mechanism that may account for the formation of the species 12, 13, and 13' is proposed.     

Synthesis of a bimetallic platinum-tungsten complex with a bridging micro-diboranyl-oxycarbyne moiety

The novel bimetallic micro-diboranyl-oxycarbyne bridged platinum-tungsten complex [W{eta(1),micro-CO-B(NMe(2))-B(NMe(2))-(eta(5)-C(5)H(4))}(CO)(2){Pt(PPh(3))(2)}] (W-Pt) () has been synthesised by a two-step reaction, starting from the dilithiated half-sandwich compound Li[W(eta(5)-C(5)H(4)Li)(CO)(3)] () via the ansa-diboranyl-oxycarbyne tungsten complex [W{eta(1)-CO-B(NMe(2))B(NMe(2))(eta(5)-C(5)H(4))}(OC)(2)] () by use of stoichiometric amounts of B(2)(NMe(2))(2)Br(2) and [Pt(eta(2)-C(2)H(4))(PPh(3))(2)], respectively.     

Homo- and heteropolynuclear platinum complexes stabilized by dimethylpyrazolato and alkynyl bridging ligands: synthesis, structures, and luminescence

This work describes the synthesis of cis-[Pt(C[triple bond]CPh)2(Hdmpz)2] (1) and its use as a precursor for the preparation of homo- and heteropolynuclear complexes. Double deprotonation of compound 1 with readily available M(I) (M = Cu, Ag, Au) or M(II) (M = Pd, Pt) species affords the discrete hexanuclear clusters [{PtM2(mu-C[triple bond]CPh)2(mu-dmpz)(2)}(2)] [M = Cu (2), Ag (3), Au (4)], in which both "Pt(C[triple bond]CPh)2(dmpz)(2)" fragments are connected by four d(10) metal centers, and are stabilized by alkynyl and dimethylpyrazolate bridging ligands, or the trinuclear complexes [Pt(mu-C[triple bond]CPh)2(mu-dmpz)(2){M(C/\P)}2] (M = Pd (5), Pt (6); C/\P = CH(2)-C(6)H(4)-P(o-tolyl)2-kappaC,P), respectively. The X-ray structures of complexes 1-4 and 6 are reported. The X-ray structure of the platinum-copper derivative 2 shows that all copper centers exhibit similar local geometry being linearly coordinated to a nitrogen atom and eta(2) to one alkynyl fragment. However in the related platinum-silver (3) and platinum-gold (4) derivatives the silver and gold atoms present three different coordination environments. The complexes have been studied by absorption and emission spectroscopy. The hexanuclear complexes exhibit bright luminescence in the solid state and in fluid solution (except 4 in the solid state at 298 K). Dual long-lived emission is observed, being clearly resolved in low-temperature rigid media. The low-energy emission is ascribed to MLM'CT Pt(d)/pi(C[triple bond]CPh)-->Pt(p(z))/M'(sp)/pi*(C[triple bond]CPh) modified by metal-metal interactions whereas the high-energy emission is tentatively attributed to an emissive state derived from dimethylpyrazolate-to-metal (d(10)) LM'CT transitions pi(dmpz)-->M'(d(10)).