Mechanistic studies of O2 reduction effected by group 9 bimetallic hydride complexes

Synthetic and kinetic studies are used to uncover mechanistic details of the reduction of O(2) to water mediated by dirhodium complexes. The mixed-valence Rh(2)(0,II)(tfepma)(2)(CN(t)Bu)(2)Cl(2) (1, tfepma = MeN[P(OCH(2)CF(3))(2)](2), CN(t)Bu = tert-butyl isocyanide) complex is protonated by HCl to produce Rh(2)(II,II)(tfepma)(2)(CN(t)Bu)(2)Cl(3)H (2), which promotes the reduction of O(2) to water with concomitant formation of Rh(2)(II,II)(tfepma)(2)(CN(t)Bu)(2)Cl(4) (3). Reactions of the analogous diiridium complexes permit the identification of plausible reaction intermediates. Ir(2)(0,II)(tfepma)(2)(CN(t)Bu)(2)Cl(2) (4) can be protonated to form the isolable complex Ir(2)(II,II)(tfepma)(2)(CN(t)Bu)(2)Cl(3)H (5), which reacts with O(2) to form Ir(2)(II,II)(tfepma)(2)(CN(t)Bu)(2)Cl(3)(OOH) (6). In addition, 4 reacts with O(2) to form Ir(2)(II,II)(tfepma)(2)(CN(t)Bu)(2)Cl(2)(η(2)-O(2)) (7), which can be protonated by HCl to furnish 6. Complexes 6 and 7 were both isolated in pure form and structurally and spectroscopically characterized. Kinetics examination of hydride complex 5 with O(2) and HCl furnishes a rate law that is consistent with an HCl-elimination mechanism, where O(2) binds an Ir(0) center to furnish an intermediate η(2)-peroxide intermediate. Dirhodium congener 2 obeys a rate law that not only is also consistent with an analogous HCl-elimination mechanism but also includes terms indicative of direct O(2) insertion and a unimolecular isomerization prior to oxygenation. The combined synthetic and mechanistic studies bespeak to the importance of peroxide and hydroperoxide intermediates in the reduction of O(2) to water by dirhodium hydride complexes.     

Oxygen reduction to water mediated by a dirhodium hydrido-chloride complex

The two-electron mixed-valence dirhodium complex Rh(2)(0,II)(tfepma)(2)(CN(t)Bu)(2)Cl(2) (tfepma = CH(3)N[P(OCH(2)CF(3))(2)](2)) reacts with HCl to furnish two isomeric dirhodium hydrido-chloride complexes, Rh(2)(II,II)(tfepma)(2)(CN(t)Bu)(2)Cl(3)H. In the presence of HCl, the hydride complex effects the reduction of 0.5 equiv of O(2) to 1 equiv of H(2)O, generating Rh(2)(II,II)(tfepma)(2)(CN(t)Bu)(2)Cl(4), which can be prepared independently by chlorine oxidation of the Rh(2)(0,II) precursor. The starting Rh(2)(0,II) complex is regenerated photochemically to close an oxygen-to-water reduction photocycle.     

A photocycle for hydrogen production from two-electron mixed-valence complexes

Dihydrides of the formula Rh2(II,II)(tfepma)3H2Cl2 (tfepma = (bis[bis(trifluoroethoxy)phosphino]methylamine, MeN(P[OCH2CF3]2)2), have been prepared by the addition of H2 to the two-electron mixed-valence complex, Rh2(0,II)(tfepma)3Cl2 (1). Three isomeric forms with hydrides in syn (2), anti (3), and cis (4) conformations have been characterized by X-ray diffraction. Photolysis of 2 results in prompt formation of a short-lived blue photoproduct (lambda(max) = 600 nm) and a stoichiometric quantity of H2, as determined by Toepler pump and isotopic labeling experiments. The blue photoproduct was identified as a Rh2(I,I) complex resulting from the reductive elimination of H2, as determined from the examination of bimetallic cores coordinated by tfepm (tfepm = (bis[bis(trifluoroethoxy)phosphino]methane, CH2(P[OCH2CF3]2)2), for which complexes of the formula M2(I,I)(tfepm)3Cl2 (5, M = Rh and 6, M = Ir) have been isolated. The d8...d8 dimer of 5 converts to Rh2(0,II)(tfepm)3Cl2CN(t)Bu (8) upon the addition of 1 equiv of tert-butylisonitrile, a result of halogen migration and disproportionation of the valence symmetric core of 5, which is structurally compared to its two-electron mixed-valence analogue, Rh2(0,II)(dfpma)3Cl2CN(t)Bu (9) (dfpma = bis(difluorophosphino)methylamine, MeN(PF2)2). The halogen migration is captured in Ir2(I,I)(tfepm)3(mu-Cl)Cl (7), which is distinguished by the presence of a chloride that bridges the diiridium centers. Taken together, complexes 1-9 permit the construction of a complete photocycle for the photogeneration of H2 by dirhodium dfpma complexes in homogeneous solutions of hydrohalic acids.     

O(2) Insertion into Group 9 Metal-Hydride Bonds: Evidence for Oxygen Activation through the Hydrogen-Atom-Abstraction Mechanism

A detailed density functional study was performed to examine the reaction of mixed-valence dirhodium and diiridium species [M(2)(0,II)(tfepma)(2)(CN(t)Bu)(2)(Cl)(2) (1, tfepma = MeN[P(OCH(2)CF(3))(2)](2), CN(t)Bu = tert-butyl isocyaninde)] with HCl and oxygen with an interest in examining the pathways for oxygen insertion into the intermediate metal hydride to form hydroperoxo species. The O(2) hydrogen atom abstraction mechanism for both the Rh and Ir was found to be feasible. This is the first time this mechanism has been applied to a Rh system and only the second time it has been examined for a system other than Pd. The competing trans HCl reductive elimination pathway was also examined and found to be greatly dependent on the stereochemistry of the starting hydride primarily due to the intermediate formed upon the loss of Cl(-). As a result, the reductive elimination pathway was more favorable by 11.5 kcal/mol for the experimentally observed Ir stereoisomer, while the two pathways were isoenergetic for the other stereoisomer of the Rh complex. All findings are consistent with the kinetics study previously performed.     

Stability-enhanced hydrogen-evolving dirhodium photocatalysts through ligand modification

The two-electron mixed-valent complex Rh(2)(0,II)(tfepma)(2)(CN(t)Bu)(2)Cl(2) (tfepma = CH(3)N[P(OCH(2)CF(3))(2)](2)) photocatalytically splits HCl to generate H(2). Whereas this catalyst degrades rapidly, with H(2) production ceasing after about 36 hours (3 turnovers), a modified complex, Rh(2)(0,II)(tfepma)(2)(CNAd)(2)Cl(2) (CNAd = 1-adamantylisocyanide) displays enhanced stability with sustained H(2) production continuing for >144 h (7 turnovers).     

Halogen oxidation and halogen photoelimination chemistry of a platinum-rhodium heterobimetallic core

The heterobimetallic complexes, PtRh(tfepma)(2)(CN(t)Bu)X(3) (X = Cl, Br), are assembled by the treatment of Pt(cod)X(2) (cod =1,5-cyclooctadiene) with {Rh(cod)X}(2), in the presence of tert-butylisonitrile (CN(t)Bu) and tfepma (tfepma = bis(trifluoroethoxyl)phosphinomethylamine). The neutral complexes contain Pt-Rh single bonds with metal-metal separations of 2.6360(3) and 2.6503(7) ? between the square planar Pt and octahedral Rh centers for the Cl and Br complexes, respectively. Oxidation of the XPt(I)Rh(II)X(2) cores with suitable halide sources (PhICl(2) or Br(2)) furnishes PtRh(tfepma)(2)(CN(t)Bu)X(5), which preserves a Pt-Rh bond. For the chloride system, the initial oxidation product orients the platinum-bound chlorides in a meridional geometry, which slowly transforms to a facial arrangement in pentane solution as verified by X-ray crystal analysis. Irradiation of the mer- or fac-Cl(3)Pt(III)Rh(II)Cl(2) isomers with visible light in the presence of olefin promotes the photoelimination of halogen and regeneration of the reduced ClPt(I)Rh(II)Cl(2) core. In addition to exhibiting photochemistry similar to that of the chloride system, the oxidized bromide cores undergo thermal reduction chemistry in the presence of olefin with zeroth-order olefin dependence. Owing to an extremely high photoreaction quantum yield for the fac-ClPt(I)Rh(II)Cl(2) isomer, details of the X(2) photoelimination have been captured by transient absorption spectroscopy. We now report the first direct observation of the photointermediate that precedes halogen reductive elimination. The intermediate is generated promptly upon excitation (<8 ns), and halogen is eliminated from it with a rate constant of 3.6 × 10(4) s(-1). As M-X photoactivation and elimination is the critical step in HX splitting, these results establish a new guidepost for the design of HX splitting cycles for solar energy storage.     

Synthesis and structural characterization of [kappa3-B,S,S-B(mimR)3]Ir(CO)(PPh3)H (R = Bu(t), Ph) and [kappa4-B(mim(Bu(t))3]M(PPh3)Cl (M = Rh, Ir): analysis of the bonding in metal borane compounds

A series of iridium and rhodium complexes that feature M-->B dative bonds, namely [kappa(3)-B,S,S-B(mim(R))3]Ir(CO)(PPh3)H (R = But, Ph) and [kappa4-B(mim(Bu)t)3]M(PPh3)Cl (M = Rh, Ir), has been synthesized via (i) the reactions of Ir(PPh3)2(CO)Cl with [Tm(Bu)t]Tl and [Tm(Ph)]Li and (ii) the reactions of (COD)M(PPh3)Cl with [Tm(Bu)t]K. The complexes have been structurally characterized by X-ray diffraction, thereby demonstrating the presence of a M-->B dative bond in each complex. The nature of the M-->B interaction in these complexes has been addressed by computational methods which indicate that the metal centers possess a d(6) configuration. The d(6) configuration is in accord with the value predicted by using a method that employs the valence to determine d(n)(), but is not in accord with the d8 configuration that is predicted using the oxidation number. Thus, even though B(mim(R))3 may be regarded as a neutral closed-shell ligand, coordination to a d(n) transition metal via the boron results in the formation of a complex in which the metal center possesses a d(n-2) configuration.     

Reactivity of novel N,N'-diphosphino-silanediamine-based rhodium(I) derivatives

The coordination abilities of the novel N,N'-diphosphino-silanediamine ligand of formula SiMe(2)(NtolPPh(2))(2) (SiNP, 1) have been investigated toward rhodium, and the derivatives [RhCl(SiNP)](2) (2), [Rh(SiNP)(COD)][BF(4)] (3), and Rh(acac)(SiNP) (4) have been synthesized. The stability of the dinuclear frame of [RhCl(SiNP)](2) (2) toward incoming nucleophiles has been shown to be dependent on their π-acceptor ability. Indeed, the mononuclear complexes RhCl(SiNP)(L) (L = CO, 5; CN(t)Bu, 6) have been isolated purely and quantitatively upon reaction of 2 with CO and CN(t)Bu, respectively. Otherwise, PPh(3) and RhCl(SiNP) equilibrate with Rh(Cl)(SiNP)(PPh(3)) (7). Carbon electrophiles such as MeI and 3-chloro-1-proprene afforded the oxidation of rhodium(I) to rhodium(III) and the formation of RhCl(2)(η(3)-C(3)H(5))(SiNP) (8) and Rh(Me)(I)(SiNP)(acac) (10), respectively. The methyl derivative 10 is thermally stable and does not react either with CO or with CN(t)Bu even in excess. Otherwise, RhCl(2)(η(3)-C(3)H(5))(SiNP) (8) is thermally stable but reacts with CO, affording 3-chloro-1-proprene and RhCl(SiNP)(CO) (5). Finally, upon reaction of Rh(acac)(SiNP) (4) and 3-chloro-1-proprene, RhCl(acac)(η(1)-C(3)H(5))(SiNP) (9a) and [Rh(acac)(η(3)-C(3)H(5))(SiNP)]Cl (9b) could be detected at 233 K. At higher temperatures, 9a and 9b smoothly decompose, affording the dinuclear derivative [RhCl(SiNP)](2) (2) and the CC coupling product 3-allylpentane-2,4-dione.     

Linear metal-metal-bonded tetranuclear M-Mo-Mo-M complexes (M = Ir and Rh): oxidative metal-metal bond formation in a tetrametallic system and 1,4-addition reaction of alkyl halides

Reaction of Mo2(pyphos)4 (1) with [MCl(CO)2]2 (M = Ir and Rh) afforded linear tetranuclear complexes of a formula Mo2M2(CO)2(Cl)2(pyphos)4 (2, M = Ir; 3, M = Rh). X-ray diffraction studies confirmed that two "MCl(CO)" fragments are introduced into both axial sites of the Mo2 core in 1 and coordinated by two PPh2 groups in a trans fashion, thereby forming a square-planar geometry around each M(I) metal. Treatment of 2 and 3 with an excess amount of tBuNC and XylNC induced dissociation of the carbonyl and chloride ligands to yield the corresponding dicationic complexes [Mo2M2(pyphos)4(tBuNC)4](Cl)2 (5a, M = Ir; 6a, M = Rh) and [Mo2M2(pyphos)4(XylNC)4](Cl)2 (7, M = Ir; 8, M = Rh). Their molecular structures were characterized by spectroscopic data as well as X-ray diffraction studies of BPh4 derivatives [Mo2M2(pyphos)4(tBuNC)4](BPh4)2 (5b, M = Ir; 6c, M = Rh), which confirmed that there is no direct sigma-bonding interaction between the M(I) atom and the Mo2 core. The M(I) atom in 5 and 6 can be oxidized by either 2 equiv of [Cp2Fe][PF6] or an equimolar amount of I2 to afford Mo(II)2M(II)2 complexes, [Mo2M2(X)2(tBuNC)4(pyphos)4]2+ in which two Mo-M(II) single bonds are formed and the bond order of the Mo-Mo moiety has been decreased to three. The Ir(I) complex 5a reacted not only with methyl iodide but also with dichloromethane to afford the 1,4-oxidative addition products [Mo2Ir2(CH3)(I)(tBuNC)4(pyphos)4](Cl)2 (13) and [Mo2Ir2(CH2Cl)(Cl)(tBuNC)4(pyphos)4](Cl)2 (15), respectively, although the corresponding reactions using the Rh(I) analogue 6 did not proceed. Kinetic analysis of the reaction with CH3I suggested that the 1,4-oxidative addition to the Ir(I) complex occurs in an SN2 reaction mechanism.     

Rhodium-103 NMR of [Rh(X)(PPh3)3] [X = Cl, N3, NCO, NCS, N(CN)2, NCBPh3, CNBPh3, CN] and derivatives containing CO, isocyanide, pyridine, H2 and O2. Ligand, solvent and temperature effects

Rhodium-103 chemical shifts are reported for 62 compounds, namely [Rh(X)(PPh3)3] [X = Cl, N3, NCO, NCS, N(CN)2, NCBPh3, CNBPh3, CN] and derivatives formed by replacement of a phosphine by CO, xylyl isocyanide (XNC) and pyridine and/or by oxidative addition of H2 or O2 to give trans-[Rh(X)(PPh3)2(CO)] (delta in the range -816 to -368 ppm) trans-[Rh(X)(PPh3)2(XNC)] (delta -817 to -250 ppm), cis-[Rh(X)(PPh3)2(py)] (the trans isomer is formed with X = CN, CNBPh3) (delta -233 to 170 ppm), [Rh(X)(H)2(PPh3)3] (delta -611 to 119), trans-[Rh(X)(H)2(PPh3)2(py)] (delta -30 to 566 ppm), [Rh(X)(O2)(PPh3)3] (delta 1393 to 3273 ppm) and cis-[Rh(X)(O2)(PPh3)2(py)] (delta 1949 to 3374 ppm). For the majority of these compounds data were obtained from solutions in chloroform and in toluene at temperatures of 247 and 300 K; for [Rh(X)(PPh3)3] (delta -562 to -4 ppm) data are reported at a number of temperatures in the range 195-300 K for solutions in chloroform, toluene and dichloromethane and at 300 K for solutions in DMSO. The expected trend to lower delta(103Rh) with decreasing temperature (vibrational shielding) is observed for the dichloromethane data, but data from solutions {of [Rh(X)(PPh3)3]} in chloroform and toluene show a number of features which diverge from this pattern, i.e. shifts to higher delta are found to accompany a decrease in temperature, most noticeably where X = CN and Cl [on changing the solvent from dichloromethane to chloroform changes in delta(103Rh) of up to 172 ppm are observed]. These results are interpreted in terms of a hydrogen-bonded interaction with the solvent that is enhanced by the presence of a polarizable ligand (CN, Cl). With a ligand (O2CCF3) that is only weakly polarizable the solvent dependence of delta(103Rh) is minimal.     

Ruthenium(II) polypyridyl complexes: potential precursors, metalloligands, and topo II inhibitors

Neutral and cationic mononuclear complexes containing both group 15 and polypyridyl ligands [Ru(kappa3-tptz)(PPh3)Cl2] [1; tptz=2,4,6-tris(2-pyridyl)-1,3,5-triazine], [Ru(kappa3-tptz)(kappa2-dppm)Cl]BF4 [2; dppm=bis(diphenylphosphino)methane], [Ru(kappa3-tptz)(PPh3)(pa)]Cl (3; pa=phenylalanine), [Ru(kappa3-tptz)(PPh3)(dtc)]Cl (4; dtc=diethyldithiocarbamate), [Ru(kappa3-tptz)(PPh3)(SCN)2] (5) and [Ru(kappa3-tptz)(PPh3)(N3)2] (6) have been synthesized. Complex 1 has been used as a metalloligand in the synthesis of homo- and heterodinuclear complexes [Cl2(PPh3)Ru(micro-tptz)Ru(eta6-C6H6)Cl]BF4 (7), [Cl2(PPh3)Ru(mu-tptz)Ru(eta6-C10H14)Cl]PF6 (8), and [Cl2(PPh3)Ru(micro-tptz)Rh(eta5-C5Me5)Cl]BF4 (9). Complexes 7-9 present examples of homo- and heterodinuclear complexes in which a typical organometallic moiety [(eta6-C6H6)RuCl]+, [(eta6-C10H14)RuCl]+, or [(eta5-C5Me5)RhCl]+ is bonded to a ruthenium(II) polypyridine moiety. The complexes have been fully characterized by elemental analyses, fast-atom-bombardment mass spectroscopy, NMR (1H and 31P), and electronic spectral studies. Molecular structures of 1-3, 8, and 9 have been determined by single-crystal X-ray diffraction analyses. Complex 1 functions as a good precursor in the synthesis of other ruthenium(II) complexes and as a metalloligand. All of the complexes under study exhibit inhibitory effects on the Topoisomerase II-DNA activity of filarial parasite Setaria cervi and beta-hematin/hemozoin formation in the presence of Plasmodium yoelii lysate.     

Synthesis, structure, and reactivity of rhodium and iridium complexes of the chelating bis-sulfoxide tBuSOC2H4SOtBu. Selective O-H activation of 2-hydroxy-isopropyl-pyridine

The chloro-bridged rhodium and iridium complexes [M2(BTSE)2Cl2] (M = Rh 1, Ir 2) bearing the chelating bis-sulfoxide tBuSOC2H4SOtBu (BTSE) were prepared by the reaction of [M2(COE)4Cl2] (M = Rh, Ir; COE = cyclooctene) with an excess of a racemic mixture of the ligand. The cationic compounds [M(BTSE)2][PF6] (M = Rh 3, Ir 4), bearing one S- and one O-bonded sulfoxide, were also obtained in good yields. The chloro-bridges in 2 can be cleaved with 2-methyl-6-pyridinemethanol and 2-aminomethyl pyridine, resulting in the iridium(I) complexes [Ir(BTSE)(Py)(Cl)] (Py = 2-methyl-6-pyridinemethanol 5, 2-aminomethyl-pyridine 6). In case of the bulky 2-hydroxy- isopropyl-pyridine, selective OH oxidative addition took place, forming the Ir(III)-hydride [Ir(BTSE)(2-isopropoxy-pyridine)(H)(Cl)] 7, with no competition from the six properly oriented C-H bonds. The cationic rhodium(I) and iridium(I) compounds [M(BTSE)(2-aminomethyl-pyridine)][X] (M = Rh 8, Ir 10), [Rh(BTSE)(2-hydroxy- isopropyl-pyridine)][X] 9(stabilized by intramolecular hydrogen bonding), [Ir(BTSE)(pyridine)2][PF6] 12, [Ir(BTSE)(alpha-picoline)2][PF6] 13, and [Rh(BTSE)(1,10-phenanthroline)][PF6] 14 were prepared either by chloride abstraction from the dimeric precursors or by replacement of the labile oxygen bonded sulfoxide in 3 or 4. Complex 14 exhibits a dimeric structure in the solid state by pi-pi stacking of the phenanthroline ligands.     

Synthesis and Structures of RhI and IrI Complexes Supported by N‐Heterocyclic Carbene‐Phosphinidene Adducts

N‐Heterocyclic carbene‐phosphinidene adducts of the type (IDipp)PR [R = Ph ( 5 ), SiMe₃ ( 6 ); IDipp = 1,3‐bis(2,6‐diisopropylphenyl)imidazolin‐2‐ylidene] were used as ligands for the preparation of rhodium(I) and iridium(I) complexes. Treatment of (IDipp)PPh ( 5 ) with the dimeric complexes [M(μ‐Cl)(COD)]₂ (M = Rh, Ir; COD = 1,5‐cyclcooctadiene) afforded the corresponding metal(I) complexes [M(COD)Cl{(IDipp)PPh}] [M = Rh ( 7 ) or Ir ( 8 )] in moderate to good yields. The reaction of (IDipp)PSiMe₃ ( 6 ) with [Ir(μ‐Cl)(COD)]₂ did not yield trimethylsilyl chloride elimination product, but furnished the 1:1 complex, [Ir(COD)Cl{(IDipp)PSiMe₃}] ( 9 ). Additionally, the rhodium‐COD complex 7 was converted into the corresponding rhodium‐carbonyl complex [Rh(CO)₂Cl{(IDipp)PPh}] ( 10 ) by reaction with an excess of carbon monoxide gas. All complexes were fully characterized by NMR spectroscopy, microanalyses, and single‐crystal X‐ray diffraction studies.     

Water addition to a two-electron mixed-valence bimetallic center

Water adds to the two-electron mixed-valence Ir(0,II)(2) core of Ir(2)(tfepma)(3)Cl(2)(tfepma = MeN[P(OCH(2)CF(3))(2)](2)) to cleanly generate an Ir(I,III)(2) hydride. Dehydrohalogenation across the Ir-Ir bond returns the complex to an Ir(0,II)(2) species.     

Cyclodiphosphazanes with hemilabile ponytails: synthesis, transition metal chemistry (Ru(II), Rh(I), Pd(II), Pt(II)), and crystal and molecular structures of mononuclear (Pd(II), Rh(I)) and bi- and tetranuclear rhodium(I) complexes

Cyclodiphosphazanes having hemilabile ponytails such as cis-[(t)()BuNP(OC(6)H(4)OMe-o)](2) (2), cis-[(t)()BuNP(OCH(2)CH(2)OMe)](2) (3), cis-[(t)BuNP(OCH(2)CH(2)SMe)](2) (4), and cis-[(t)BuNP(OCH(2)CH(2)NMe(2))](2) (5) were synthesized by reacting cis-[(t)()BuNPCl](2) (1) with corresponding nucleophiles. The reaction of 2 with [M(COD)Cl(2)] afforded cis-[MCl(2)(2)(2)] derivatives (M = Pd (6), Pt (7)), whereas, with [Pd(NCPh)(2)Cl(2)], trans-[MCl(2)(2)(2)] (8) was obtained. The reaction of 2 with [Pd(PEt(3))Cl(2)](2), [{Ru(eta(6)-p-cymene)Cl(2)](2), and [M(COD)Cl](2) (M = Rh, Ir) afforded mononuclear complexes of Pd(II) (9), Ru(II) (11), Rh(I) (12), and Ir(I) (13) irrespective of the stoichiometry of the reactants and the reaction condition. In the above complexes the cyclodiphosphazane acts as a monodentate ligand. The reaction of 2 with [PdCl(eta(3)-C(3)H(5))](2) afforded binuclear complex [(PdCl(eta(3)-C(3)H(5)))(2){((t)BuNP(OC(6)H(4)OMe-o))(2)-kappaP}] (10). The reaction of ligand 3 with [Rh(CO)(2)Cl](2) in 1:1 ratio in CH(3)CN under reflux condition afforded tetranuclear rhodium(I) metallamacrocycle (14), whereas the ligands 4 and 5 afforded bischelated binuclear complexes 15 and 16, respectively. The crystal structures of 8, 9, 12, 14, and 16 are reported.     

Synthesis and characterisation of cyanodithioimidocarbonate [C2N2S2]2- complexes

[PPh4]2[M(C2N2S2)2](M = Pt, Pd) and [Pt(C2N2S2)(PR3)2](PR3= PMe2Ph, PPh3) and [Pt(C2N2S2)(PP)](PP = dppe, dppm, dppf) were all obtained by the reaction of the appropriate metal halide containing complex with potassium cyanodithioimidocarbonate. The dimeric cyanodithioimidocarbonate complexes [[Pt(C2N2S2)(PR3)]2](PR3 = PMe2Ph), [M[(C2N2S2)(eta5-C5Me5)]2](M = Rh, Ir)and [[Ru(C2N2S2)(eta6-p-MeC6H4iPr)]2] have been synthesised from the appropriate transition metal dimer starting material. The cyanodithioimidocarbonate ligand is S,S and bidentate in the monomeric complexes with the terminal CN group being approximately coplanar with the CS2 group and trigonal at nitrogen thus reducing the planar symmetry of the ligand. In the dimeric compound one of the sulfur atoms bridges two metal atoms with the core exhibiting a cubane-like geometry.     

Alkylthio bridged 44 cve triangular platinum clusters: synthesis, oxidation, degradation, ligand substitution, and quantum chemical calculations

Acetylplatinum(II) complexes trans-[Pt(COMe)Cl(L)2] (L = PPh3, 2a; P(4-FC6H4)3, 2b) were found to react with dialkyldisulfides R2S2 (R = Me, Et, Pr, Bu; Pr = n-propyl, Bu = n-butyl), yielding trinuclear 44 cve (cluster valence electrons) platinum clusters [(PtL)3(mu-SR)3]Cl (4). The analogous reaction of 2a-b with Ph2S2 gave SPh bridged dinuclear complexes trans-[{PtCl(L)}2(mu-SPh)2] (5), whereas the addition of Bn2S2 (Bn = benzyl) to 2a ended up in the formation of [{Pt(PPh3)}3(mu3-S)(mu-SBn)3]Cl (6). Theoretical studies based on the AIM theory revealed that type 4 complexes must be regarded as triangular platinum clusters with Pt-Pt bonds whereas complex 6 must be treated as a sulfur capped 48 ve (valence electrons) trinuclear platinum(II) complex without Pt-Pt bonding interactions. Phosphine ligands with a lower donor capability in clusters 4 proved to be subject to substitution by stronger donating monodentate phosphine ligands (L' = PMePh2, PMe2Ph, PBu3) yielding clusters [(PtL')3(mu-SR)3]Cl (9). In case of the reaction of clusters 4 and 9 with PPh2CH2PPh2 (dppm), a fragmentation reaction occurred, and the complexes [(PtL)2(mu-SMe)(mu-dppm)]Cl (12) and [Pt(mu-SMe)2(dppm)] (13) were isolated. Furthermore, oxidation reactions of cluster [{Pt(PPh3)}3(mu-SMe)3]Cl (4a) using halogens (Br2, I2) gave dimeric platinum(II) complexes cis-[{PtX(PPh3)}2(mu-SMe)2] (14, X = Br, I) whereas oxidation reactions using sulfur and selenium afforded chalcogen capped trinuclear 48 ve complexes [{Pt(PPh3)}3(mu3-E)(mu-SMe)3] (15, E = S, Se). All compounds were fully characterized by means of NMR and IR spectroscopy, microanalyses, and ESI mass spectrometry. Furthermore, X-ray diffraction analyses were performed for the triangular cluster 4a, the trinuclear complex 6, as well as for the dinuclear complexes trans-[{Pt(AsPh3)}2(mu-SPh)2] (5c), [{Pt(PPh3)}2(mu-SMe)(mu-dppm)]Cl (12a), and [{{PtBr(PPh3)}2(mu-SMe)2] (14a).     

NMR studies on the novel heterobimetallic complexes [M(dppm)(Ph(2)PCH(2)PPh(2)PPPP) {Pt(PPh3)2}]OTf (M = Rh, Ir) derived from the stepwise activation of white phosphorus

The solution structures of the novel heterobimetallic complexes [Ir(dppm)(Ph(2)PCH(2)PPh(2)PPPP){Pt(PPh(3))2}]OTf and [Rh(dppm)(Ph(2)PCH(2)PPh(2)PPPP){Pt(PPh(3))(2)}]OTf derived from the reaction of Rh and Ir--P(5) precursors with [Pt(C2H4)(PPh3)2] have been unambiguously assigned on the basis of 1H NMR and 31P{1H} NMR data. The results are in agreement with the regio-selective insertion of the {Pt(PPh3)2} moiety resulting in a new pentaphosphorus topology which agrees with the formal formation of a unique phosphonium(+)-tetraphosphabutadienide(2-) ligand.     

Synthesis and reactivity of Ir(I) and Ir(III) complexes with MeNH2, Me2C=NR (R = H, Me), C,N-C6H4{C(Me)=N(Me)}-2, and N,N'-RN=C(Me)CH2C(Me2)NHR (R = H, Me) ligands

Complexes [Ir(Cp*)Cl(n)(NH2Me)(3-n)]X(m) (n = 2, m = 0 (1), n = 1, m = 1, X = Cl (2a), n = 0, m = 2, X = OTf (3)) are obtained by reacting [Ir(Cp*)Cl(mu-Cl)]2 with MeNH2 (1:2 or 1:8) or with [Ag(NH2Me)2]OTf (1:4), respectively. Complex 2b (n = 1, m = 1, X = ClO 4) is obtained from 2a and NaClO4 x H2O. The reaction of 3 with MeC(O)Ph at 80 degrees C gives [Ir(Cp*){C,N-C6H4{C(Me)=N(Me)}-2}(NH2Me)]OTf (4), which in turn reacts with RNC to give [Ir(Cp*){C,N-C6H4{C(Me)=N(Me)}-2}(CNR)]OTf (R = (t)Bu (5), Xy (6)). [Ir(mu-Cl)(COD)]2 reacts with [Ag{N(R)=CMe2}2]X (1:2) to give [Ir{N(R)=CMe2}2(COD)]X (R = H, X = ClO4 (7); R = Me, X = OTf (8)). Complexes [Ir(CO)2(NH=CMe2)2]ClO4 (9) and [IrCl{N(R)=CMe2}(COD)] (R = H (10), Me (11)) are obtained from the appropriate [Ir{N(R)=CMe2}2(COD)]X and CO or Me4NCl, respectively. [Ir(Cp*)Cl(mu-Cl)]2 reacts with [Au(NH=CMe2)(PPh3)]ClO4 (1:2) to give [Ir(Cp*)(mu-Cl)(NH=CMe2)]2(ClO4)2 (12) which in turn reacts with PPh 3 or Me4NCl (1:2) to give [Ir(Cp*)Cl(NH=CMe2)(PPh3)]ClO4 (13) or [Ir(Cp*)Cl2(NH=CMe2)] (14), respectively. Complex 14 hydrolyzes in a CH2Cl2/Et2O solution to give [Ir(Cp*)Cl2(NH3)] (15). The reaction of [Ir(Cp*)Cl(mu-Cl)]2 with [Ag(NH=CMe2)2]ClO4 (1:4) gives [Ir(Cp*)(NH=CMe2)3](ClO4)2 (16a), which reacts with PPNCl (PPN = Ph3=P=N=PPh3) under different reaction conditions to give [Ir(Cp*)(NH=CMe2)3]XY (X = Cl, Y = ClO4 (16b); X = Y = Cl (16c)). Equimolar amounts of 14 and 16a react to give [Ir(Cp*)Cl(NH=CMe2)2]ClO4 (17), which in turn reacts with PPNCl to give [Ir(Cp*)Cl(H-imam)]Cl (R-imam = N,N'-N(R)=C(Me)CH2C(Me)2NHR (18a)]. Complexes [Ir(Cp*)Cl(R-imam)]ClO4 (R = H (18b), Me (19)) are obtained from 18a and AgClO4 or by refluxing 2b in acetone for 7 h, respectively. They react with AgClO4 and the appropriate neutral ligand or with [Ag(NH=CMe2)2]ClO4 to give [Ir(Cp*)(R-imam)L](ClO4)2 (R = H, L = (t)BuNC (20), XyNC (21); R = Me, L = MeCN (22)) or [Ir(Cp*)(H-imam)(NH=CMe2)](ClO4)2 (23a), respectively. The later reacts with PPNCl to give [Ir(Cp*)(H-imam)(NH=CMe2)]Cl(ClO4) (23b). The reaction of 22 with XyNC gives [Ir(Cp*)(Me-imam)(CNXy)](ClO4)2 (24). The structures of complexes 15, 16c and 18b have been solved by X-ray diffraction methods.     

Ligand effects on luminescence of new type blue light-emitting mono(2-phenylpyridinato)iridium(III) complexes

Newly prepared hydrido iridium(III) complexes [Ir(ppy)(PPh3)2(H)L](0,+) (ppy = bidentate 2-phenylpyridinato anionic ligand; L = MeCN (1b), CO (1c), CN(-) (1d); H being trans to the nitrogen of ppy ligand) emit blue light at the emission lambda(max) (452-457, 483-487 nm) significantly shorter than those (468, 495 nm) of the chloro complex Ir(ppy)(PPh3)2(H)(Cl) (1a). Replacing ppy of 1a-d with F2ppy (2,4-difluoro-2-phenylpyridinato anion) and F2Meppy (2,4-difluoro-2-phenyl-m-methylpyridinato anion) brings further blue-shifts down to the emission lambda(max) at 439-441 and 465-467 nm with CIE color coordinates being x = 0.16 and y = 0.18-0.20 to display a deep-blue photoemission. No significant blue shift is observed by replacing PPh3 of 1a with PPh2Me to produce Ir(ppy)(PPh2Me)2(H)(Cl) (1aPPh 2Me), which displays emission lambda max at 467 and 494 nm. The chloro complexes, [Ir(ppy)(PPh3)2(Cl)(L)](0,+) (L = MeCN (2b), CO (2c), CN(-) (2d)) having a chlorine ligand trans to the nitrogen of ppy also emit deep-blue light at emission lambda(max) 452-457 and 482-487 nm.