  Synthesis and catalytic application of palladium imidazol(in)ium-2- dithiocarboxylate complexes; ; Delaude, Lionel  et alin Dalton Transactions (2012), 41(40), 12386-12394 The palladium(ii) dimer, [Pd(C,N-C 6H 4CH 2NMe 2)Cl] 2 reacts with two equivalents of the NHC·CS 2 zwitterionic ligands [NHC = IPr (1,3- diisopropylimidazol-2-ylidene), ICy (1,3-dicyclohexylimidazol-2 ... [more ▼] The palladium(ii) dimer, [Pd(C,N-C 6H 4CH 2NMe 2)Cl] 2 reacts with two equivalents of the NHC·CS 2 zwitterionic ligands [NHC = IPr (1,3- diisopropylimidazol-2-ylidene), ICy (1,3-dicyclohexylimidazol-2-ylidene), IMes (1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene), IDip (1,3-bis(2,6- diisopropylphenyl)imidazol-2-ylidene), SIMes (1,3-bis(2,4,6-trimethylphenyl) imidazolin-2-ylidene)] in the presence of NH 4PF 6, to yield the cationic products [Pd(C,N-C 6H 4CH 2NMe 2)(S 2C·NHC)] +. In a similar fashion, the compounds [Pd(C,N-bzq)(S 2C·NHC)] + (bzq = benzo[h]quinolinyl, NHC = ICy, IMes, IDip) are obtained from the corresponding dimer [Pd(C,N-bzq)Cl] 2. The bis(phosphine) compounds [Pd(S 2C·NHC)(PPh 3) 2] 2+ (NHC = ICy, IMes, IDip, SIMes) are obtained on treatment of [PdCl 2(PPh 3) 2] with NHC·CS 2 zwitterions in the presence of NH 4PF 6. The reaction of [PdCl 2(dppf)] with IMes·CS 2 and NH 4PF 6 provides the complex [Pd(S 2C·IMes)(dppf)] 2+. The complexes [Pd(S 2C·NHC)(PPh 3) 2](PF 6) 2 (NHC = IMes, IDip) were active pre-catalysts (1 mol% loading) for the conversion of benzo[h]quinoline to 10-methoxybenzo[h]quinoline in the presence of PhI(OAc) 2 and methanol. The intermediacy of [Pd(C,N-bzq)(S 2C·NHC)] + was supported by the high yield of 10-methoxybenzo[h]quinoline using [Pd(C,N-bzq)(S 2C·IDip)] + to promote the same reaction. Small amounts of 2,10-dimethoxybenzo[h]quinoline were also isolated from these reactions. Using [Pd(C,N-bzq)(S 2C·IDip)] + and N-chlorosuccinimide as the oxidant led to the formation of 10-chlorobenzo[h]quinoline in moderate yield from benzo[h]quinoline. The molecular structures of [Pd(S 2C·IMes)(PPh 3) 2](PF 6) 2 and [Pd(S 2C·IMes) (dppf)](PF 6) 2 were determined crystallographically. [less ▲] Detailed reference viewed: 1 (0 ULg)Gold(I) complexes bearing mixed-donor ligands derived from N-heterocyclic carbenes; ; Delaude, Lionel et alin Dalton Transactions (2011), 40(25), 6645-6658 The new 2-phenylthiocarbamoyl-1,3-dimesitylimidazolium inner salt (IMes•CSNPh) reacts with [AuCl(L)] in the presence of NH4PF6 to yield [(L)Au(SCNPh•IMes)]+ (L = PMe3, PPh3, PCy3, CNBut). The carbene ... [more ▼] The new 2-phenylthiocarbamoyl-1,3-dimesitylimidazolium inner salt (IMes•CSNPh) reacts with [AuCl(L)] in the presence of NH4PF6 to yield [(L)Au(SCNPh•IMes)]+ (L = PMe3, PPh3, PCy3, CNBut). The carbene-containing precursor [(IDip)AuCl] reacts with IMes•CSNPh under the same conditions to afford the complex [(IDip)Au(SCNPh•IMes)] + (IDip = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene). Treatment of the diphosphine complex [(dppm)(AuCl)2] with one equivalent of IMes•CSNPh yields the digold metallacycle, [(dppm)Au 2(SCNPh•IMes)]2+, while reaction of [L 2(AuCl)2] with two equivalents of IMes•CSNPh results in [(L2){Au(SCNPh•IMes)}2]2+ (L2 = dppb, dppf, or dppa; dppb = 1,4-bis(diphenylphosphino)butane, dppf = 1,1'-bis(diphenylphosphino)ferrocene, dppa = 1,4- bis(diphenylphosphino)acetylene). The homoleptic complex [Au(SCNPh•IMes) 2]+ is formed on reaction of [AuCl(tht)] (tht = tetrahydrothiophene) with two equivalents of the imidazolium-2- phenylthiocarbamoyl ligand. This product reacts with AgOTf to yield the mixed metal compound [AuAg(SCNPh•IMes)2]2+. Over time, the unusual trimetallic complex [Au(AgOTf)2(SCNPh•IMes) 2]+ is formed. The sulfur-oxygen mixed-donor ligands IMes•COS and SIMes•COS (SIMes = 1,3-bis(2,4,6-trimethylphenyl) imidazolin-2-ylidene) were used to prepare [(L)Au(SOC•IMes)]+ and [(L)Au(SOC•SIMes)]+ from [(L)AuCl] (L = PPh3, CNtBu). The bimetallic examples [(dppf){Au(SOC•IMes)} 2]2+ and [(dppf){Au(SOC•SIMes)}2] 2+ were synthesized from the reaction of [(dppf)(AuCl)2] with the appropriate ligand. Reaction of [(tht)AuCl] with one equivalent of IMes•COS or SIMes•COS yields [Au(SOC•IMes) 2]+ and [Au(SOC•SIMes)2]+, respectively. The compounds [(Ph3P)Au(SCNPh•IMes)]PF 6, [(Cy3P)Au(SCNPh•IMes)]PF6 and [Au(AgOTf)2(SCNPh•IMes)2]OTf were characterized crystallographically. [less ▲] Detailed reference viewed: 12 (4 ULg)Dithiocarboxylate complexes of ruthenium(II) and osmium(II); ; et al in Dalton Transactions (Cambridge, England : 2003) (2011), 40(14), 3737-3747 The ruthenium(II) complexes [Ru(R)(kappa(2)-S2C center dot IPr)(CO)(PPh3)(2)](+) (R = CH=CHBut, CH CHC6H4Me-4, C(C CPh)=CHPh) are formed on reaction of IPr center dot CS2 with [Ru(R)Cl(CO)(BTD)(PPh3)(2 ... [more ▼] The ruthenium(II) complexes [Ru(R)(kappa(2)-S2C center dot IPr)(CO)(PPh3)(2)](+) (R = CH=CHBut, CH CHC6H4Me-4, C(C CPh)=CHPh) are formed on reaction of IPr center dot CS2 with [Ru(R)Cl(CO)(BTD)(PPh3)(2)] (BTD = 2,1,3-benzothiadiazole) or [Ru(C(C CPh)=CHPh)Cl(CO)(PPh3)(2)] in the presence of ammonium hexafluorophosphate. Similarly, the complexes [Ru(CH=CHC6H4Me-4)(kappa(2)-S2C center dot ICy)(CO)(PPh3)(2)](+) and [Ru(C(C CPh)=CHPh)(kappa(2)-S2C center dot ICy)(CO)(PPh3)(2)](+) are formed in the same manner when ICy center dot CS2 is employed. The ligand IMes center dot CS2 reacts with [Ru(R)Cl(CO)(BTD)(PPh3)(2)] to form the compounds [Ru(R)(kappa(2)-S2C center dot IMes)(CO)(PPh3)(2)](+) (R = CH=CHBut, CH=CHC6H4Me-4, C(C CPh)=CHPh). Two osmium analogues, [Os(CH CHC(6)H4(M)e-4)(kappa(2)-S2C center dot IMes)(CO)(PPh3)(2)](+) and [Os(C(C CPh)=CHPh)(kappa(2)-S2C center dot IMes)(CO)(PPh3)(2)](+) were also prepared. When the more bulky diisopropylphenyl derivative IDip center dot CS2 is used, an unusual product, [Ru(kappa(2)-SC(H)S(CH= CHC6H4Me-4)center dot IDip)Cl(CO)(PPh3)(2)](+), with a migrated vinyl group, is obtained. Over extended reaction times, [Ru(CH=CHC6H4Me-4)Cl(BTD)(CO)(PPh3)(2)] also reacts with IMes center dot CS2 and NH4PF6 to yield the analogous product [Ru{kappa(2)-SC(H)S(CH=CHC6H4Me-4)center dot IMes}Cl(CO)(PPh3)(2)](+) via the intermediate [Ru(CH=CHC6H4Me-4)(kappa(2)-S2C center dot IMes)(CO)(PPh3)(2)](+). Structural studies are reported for [Ru(CH=CHC6H4Me-4)(kappa(2)-S2C center dot IPr)(CO)(PPh3)(2)]PF6 and [Ru(C(C CPh)=CHPh)(kappa(2)-S2C center dot ICy)(CO)(PPh3)(2)]PF6. [less ▲] Detailed reference viewed: 17 (6 ULg)The Use of Imidazolium-2-dithiocarboxylates in the Formation of Gold(l) Complexes and Gold Nanoparticles; Delaude, Lionel ; et alin Inorganic Chemistry (2010), 49(4), 1784-1793 The imidazolium-2-dithiocarboxylate ligands IPr.CS2, Mes.CS2, and IDip.CS2 react with [AuCl(PPh3)] to yield [(Ph3P)Au(S2C.IPr))(+), [(Ph3P)Au(S2C.IMes)](+), and [(Ph3P)Au(S2C-IDip)](+), respectively. The ... [more ▼] The imidazolium-2-dithiocarboxylate ligands IPr.CS2, Mes.CS2, and IDip.CS2 react with [AuCl(PPh3)] to yield [(Ph3P)Au(S2C.IPr))(+), [(Ph3P)Au(S2C.IMes)](+), and [(Ph3P)Au(S2C-IDip)](+), respectively. The compounds [(L)Au(S2C-IMes)](+) are prepared from the reaction of IMes.CS2 with [AuCl(L) (L = PMe3, PCy3, (CNBu)-Bu-t). The carbene-containing precursor [(IDip)AuCl] reacts with IPr.CS2 and IMes.CS2 to afford the complexes [(IDip)Au(S2C.IPr)](+) and [(IDip)Au(S2C.IMes)](+) with two carbene units, one bound to the metal center and the other to the dithiocarboxylate unit. Treatment of the diphosphine-gold complex [(dppm)(AuCl)(2)] with 1 equiv of IMes.CS2 yields [(dppm)Au-2(S2C.IMeS)](2+), while the reaction of [L-2(AuCl)(2)] (L-2 = dppb, dppf) with 2 equiv of IMes.CS2 results in [(L-2){Au(S2C.IMes)}(2)](2+). The homoleptic complexes [Au(S2C.IPr)(2)](2+), [Au(S2C.IMes)(2)](2+), and [Au(S2C.IDiP)(2)](2+) are obtained from the reaction of [AuCl(tht)] with 2 equiv of the appropriate imidazolium-2-dithiocarboxylate ligand. The compounds [(Ph3P)Au(S2C.NHC)](+) (NHC = IMes, IDip) and [(IDip)Au(S2C.NHC)](+) (NHC = IPr, IMes) are characterized crystallographically. The IMes.CS2 ligand is also used to prepare functionalized gold nanoparticles with diameters of 11.5 (+/-1.2) and 2.6 (+/-0.3) nm. [less ▲] Detailed reference viewed: 32 (3 ULg) |
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