Bi- and tetranuclear polyfluorophenyl-bridged gold(I) complexes

The reaction of RAuL (R = 2,4,6-C₆F₃H₂, 3,6-C₆F₂H₃, 4-C₆FH₄ or 3-CF₃C₆H₄; L = PPh₃ or AsPh₃) or RAudpeAuR with inorganic acids HA (A = ClO₄, BF₄ or PF₆) leads to binuclear complexes of the types [R(AuL)₂]A or [R(Au₂dpe)]BF₄. Similarly, reaction of NBu₄[Au(2,4,6-C₆F₃H₂)₂] with HPF₆ yields the tetranuclear complex Au₄(2,4,6-C₆F₃H₂)₄. Addition of RAuL to solutions obtained by treating ClAuL with AgA also gives compounds of the type [R(AuL)₂]A.     

Chlorobis(polyfluorophenyl)thallium(III) complexes and their reactions with gold(I) and tin(II) compounds

The reaction of TlCl₃ with RLi leads to complexes of the general formula TlR₂Cl (R = C₆F₅, p-C₆F₄H, m-C₆F₄H, 2,4,6-C₆F₃H₂, p-C₆FH₄ or m-CF₃C₆H₄). Some of these undergo oxidative addition reactions with gold(I) complexes to give polyfluorophenyl derivatives of the types AuR₂ClL and Au(C₆F₅)R₂(tht) (tht = tetrahydrothiophen), and with SnCl₂ to give oily materials from which stable solids of the general formula Q[SnR₂Cl₃] can be isolated by addition of QCl (Q = Et₄N or Ph₃BzP).     

Synthesis and Spectra of Cationic Bis(tertiary phosphine) derivatives of cycloheptatrienyliummolybdenum and cyclopentadienyliron complexes

Reaction of [(η-C₇H₇)Mo(CO)₃][PF₆] and [(η-C₅H₅)Fe(CO)₂CH₃CN][PF₆] with ditertiary phosphine ligands afforded products of three types; the monosubstituted complexes [(Ring)M(CO)₂Ph₂P(CH₂)_nPPh₂][PF₆] (Ring = η-C₇H₇, M = Mo, N = 1; Ring = η-C₅H₅, M = Fe, N = 1 and 2), the chelated complexes [(Ring)M(CO)Ph₂P(CH₂)_nPPh₂][PF₆] (Ring = η-C₇H₇, M = Mo, N = 1 and 2; Ring = η-C₅H₅, M = Fe, N = 1 and 2), and the dinuclear complex [{(η-C₇H₇)Mo(CO)₂}₂ -μ- Ph₂PCH₂CH₂PPh₂][(PF₆)₂]. Spectroscopic properties, including ³¹P NMR, are reported.     

ortho-, meta- and para-nitrophenylgold(I) complexes

Treatment of [BzPh₃P][AuCl₂] with [Hg(x-C₆H₄NO₂)₂] (x = o, m, or p) gives anionic gold(I) complexes of the type [BzPh₃P][Au(R)Cl](R = o-, m- or p-C₆H₄NO₂, Bz = C₆H₅CH₂). The chloro ligand in [Au(o-C₆H₄NO₂)Cl]^? can be replaced by bromo or iodo ligands by use of NaBr or NaI. The anions [Au(R)Cl]^? react with neutral monodentate ligands, L, to give neutral mononuclear complexes [Au(R)L] (R = o-C₆H₄NO₂, L = PPh₃, AsPh₃; R = m-C₆H₄NO₂, L = PPh₃) and with 1,2-bis(diphenylphosphino)ethane (dpe) to give [Au₂(R)₂(dpe)] (R = o-C₆H₄NO₂). The corresponding [Au(p-C₆H₄NO₂)Cl]^? reacts with PPh₃ or AsPh₃ to give mixtures containing [AuClL]. The anionic ortho-nitrophenylgold(I) complex is much more stable than its meta- or para-nitrophenyl isomers. These are thought to be the first reports of nitrophenylgold(I) complexes.     

Photoinitiated Reactions of Haloperfluorocarbons with Gold(I) Organometallic Complexes: Perfluoroalkyl Gold(I) and Gold(III) Complexes

The study of perfluoroalkyl metal complexes is key to understand and improve metal-promoted perfluoroalkylation reactions. Herein, we report the synthesis of the first gold complexes with primary or secondary perfluoroalkyl ligands by photoinitiated reactions between Au^I organometallic complexes and iodoperfluoroalkanes. Complexes of the types LAuR_F (L=PPh₃ or N,N-bis(2,6-diisopropylphenyl)imidazol-2-ylidene; R_F=n-C₄F₉, n-C₆F₁₃, i-C₃F₇, c-C₆F₁₁) and [Au(R_F)(Ar)I(PPh₃)] (Ar=2,4,6-trimethylphenyl) have been isolated and characterized. Alkynes R_FC≡CR were formed by reaction of Ph₃PAuC≡CR (R=Ph, nHex) with IR_F (R_F=n-C₄F₉, i-C₃F₇). According to the evidences obtained, this transformation undergoes through a photoinitiated radical mechanism. Au^III complexes [Au(n-C₄F₉)(X)(Y)L] (X=Y=Cl, Br, I, Me; X=Me, Y=I) have been prepared or in situ generated, and their thermal or photochemical decomposition reactions have been studied.     

Synthesis and spectra of bis(tertiaryphosphine) derivatives of cycloheptatrienyltungsten complexes

Reaction of [WI(CO)₂(η⁷-C₇H₇)] with dppm (dppm = Ph₂PCH₂PPh₂) or dppe (dppe = Ph₂PCH₂CH₂PPh₂) gives the trihaptocycloheptatrienyl complexes [WI(CO)₂(L-L)(η³-C₇H₇)] [L-L = dppm, (A₁); L-L = dppe (A₂)]. The complex A₁ reacts with NH₄PF₆ to give the unidentate biphosphine complex [W(CO)₂(dppm-P)(η⁷-C₇H₇)][PF₆] (B) which yields [W(CO)(dppm)(η⁷-C₇H₇)][PF₆] (C) on reaction with Me₃NO·2H₂O. Substitution of a carbonyl ligand in [W(CO)₃(η⁷-C₇H₇)][PF₆] with the organometallic phosphine ligand [Mo(CO)₂(dppe-P)(η⁷-C₇H₇)][PF₆] yields the heterobimetallic [{W(CO)₂(η⁷-C₇H₇)}(μ-dppe){Mo(CO)₂(η⁷-C₇H₇)}x][PF₆]₂ (D).     

Nickelocene chemistry : I. Reactions of methylenetriphenylphosphorane with η5-cyclopentadienylnickel complexes

Nickelocene reacts with methylenetriphenylphosphorane with displacement of one of the cyclopentadienyl rings to give the cation [Ni(CH₂PPh₃)₂(η⁵-C₅H₅)]⁺, which can also be obtained by reaction of the cationic complexes [Ni(η⁵-C₅H₅)L₂]X (L  PPh₃ or P-n-Bu₃) with Ph₃PCH₂. With [NiBr(η⁵-C₅H₅)(PPh₃)] the ylide displaces Br_- to form [Ni(CH₂PPh₃)(η⁵-C₅H₅)(PPh₃)] Br.     

Polynuclear palladium and gold perhalophenyl derivatives with dppm bridges. Crystal and molecular structure of trans-C6F5Au(μ-dppm)Pd(C6F5)2(μ-dppm)AuC6F5 (dppm = Ph2PCH2PPh2)

Reactions of PdRR′(η¹-dppm)₂ (R = R′= C₆F₅ or C₆Cl₅; R = C₆F₅, R′= Cl; dppm = Ph₂PCH₂PPh₂) with the gold derivatives ClAu(tht), C₆F₅Au(tht), (C₆F₅)₃Au(tht) or O₃ClOAuPPh₃ (tht = tetrahydrothiophen) in appropriate ratios yield the bi- or tri-nuclear complexes PdRR′(dppm)₂AuCl, PdRR′(dppm)₂Au(C₆F₅); PdRR′(dppm)₂Au(C₆F₅)₃; PdRR′(dppmAuCl)₂; PdRR′(dppmAuC₆F₅)₂; PdRR′[dppmAu(C₆F₅)₃]₂, [PdRR′(dppm)₂Au]X (X = ClO₄ or BPh₄); [PPh₃Au(dppm)Pd(C₆F₅)₂(dppm)AuCl]ClO₄ or [PPh₃ Au(dppm)Pd(C₆F₅)₂(dppm)Au(C₆F₅)₃]ClO₄. The structure of trans-Pd(C₆F₅)₂[dppmAu(C₆F₅)]₂ has been determined by X-ray diffraction.     

Evidence for the iron formyl (η5-C5H5)Fe(Ph2PCH2CH2PPh2)(CHO)

Evidence for (η⁵-C₅H₅)Fe(Ph₂PCH₂CH₂PPh₂)(CHO) as an intermediate in the reduction of [(η⁵-C₅H₅)Fe(Ph₂PCH₂CH₂PPh₂)CO]PF₆ to (η⁵-C₅H₅)Fe(CO)H(Ph₂PCH₂CH₂PPh₂) and for a metal-carbonyl hydride-formyl equilibrium is described.     

Nickelocene chemistry : III. Reactions of Bromo(η5-cyclopentadienyl)triphenylphosphinenickel with phosphorus,arsenic and sulphur ylids

The phosphorus ylids Ph₃PCHR (R = Me, Et, Prⁿ, Prⁱ, Bu_n, Cl, and OMe), and the ylids Ph₃AsCH₂, Me₂SCH₂, and Me₂S(O)CH₂ react with [Ni(η⁵-C₅H₅)Br(PPh₃)] at room temperature to give the complexes [Ni(Ph₃PCHR)(η⁵-C₅H₅(PPh₃)] Br, [Ni(Ph₃AsCH₂)(η⁵-C₅H₅)(PPh₃)]Br, [Ni(Me₂SCH₂)(η⁵-C₅H₅)(PPh₃)]Br and [Ni{Me₂S(O)CH₂} (η⁵-C₅H₅)(PPh₃)]Br, respectively. These are readily converted into the corresponding hexafluorophosphate salts on reaction with ammonium hexafluorophosphate. Under more forcing conditions the stabilised ylid Ph₃PCHCOPh gives a product believed to be the complex [Ni(Ph₃PCHCOPh)₂(η⁵-C₅H₅)]Br, isolated and characterised as its PF₆^? salt.     

Metal Ions in Biological Systems,Volume 4. Metal Ions as Probes; : edited by Helmut Sigel,Marcel Dekker,New York, 1974, xii + 261 pages, $24.75.

Trends in ³¹P NMR coordination shifts for the complexes M(CO)₃BrL₂, [M(CO)₃L₂(NCMe)]⁺, MeC₅H₄Mn(CO)L₂ and [MeC₅H₄Mn(CO)₂]₂L₂ (M = Mn and Re;L₂ = Ph₂PCH₂PPh₂, Ph₂PCH₂CH₂PPh₂ and Ph₂PCH₂CH₂AsPh₂) are discussed.     

Demercuriation reactions of the complexes [(PPh3)2RPtHgR′] containing platinum-mercury bonds

The compounds [(PPh₃)₂,RPtHgR′] (R = CH₃, R′= 2,5-C₆H₃Cl₂, 2,3,4- and 2,4,6-C₆H₂Cl₃, 2,3,4,5-, 2,3,4,6- and 2,3,5,6-C₆HCl₄, C₆Cl₅; R = Et, R′ = 2,5-C₆H₃Cl₂, 2,4,6-C₆H₂Cl₃; R = 2-C₆H₄Cl, R′=2-C₆H₄(CH₃)) have been prepared by the reactions of RHgR′ with Pt(PPh₃)₃, in order to study their possible use as intermediates in the preparation of diorganoplatinum complexes with different organic ligands. The dependence of J(³¹P-¹⁹⁵Pt) on slight differences in the electronic character of the ligand R′ in the series of compounds [(PPh₃)₂(CH₃)Pt-HgR′] has been studied.     

Crown compounds for anions. Unusual complex of trimetric perfluoro-o-phenylenemercury with the bromide anion having a polydecker sandwich structure

Here we show that cyclic trimetric perfluoro-o-phenylenemercury (o-C₆F₄Hg)₃ is capable of forming complexes with [PPh₄]⁺Br⁻, [PPh₃Me]⁺I⁻ and [PPh₄]⁺Cl⁻ of the composition [(o-C₆F₄Hg)₃X]⁻ [PR₃R′]⁺ (X = Br, R = R′ = Ph; X = I, R = Ph, R′ = Me) or {[(o-C₆F₄Hg)₃X₂}²⁻[PR₃R′]⁺₂ (X = Cl, R = R′ = Ph). An X-ray study of the complex with [PPh₄]⁺Br⁻ revealed that it has the unusual structure of the polydecker bent sandwich wherein each Br⁻ anion is coordinated with six mercury atoms of two neighbouring molecules of (o-C₆F₄Hg)₃.     

Crystal and molecular structures of (η-xanthene)- (η-cyclopentadienyl)iron(II) hexafluorophosphate and (η-2-methylthianthrene)(η-cyclopentadienyl)iron(II) hexafluorophosphate

The neutral complexes (η⁵-C₅H₅NiXL (X = Cl, L = PPh₃ (I); L = PCy₃ (II); X = Br, L = PPh₃ (III); L = PCy₃ (IV); X = I, L = PPh₃ (V); L = PCy₃ (VI)) have been obtained by treating NiX₂L₂ with thallium cyclopentadienide. The same reaction in the presence of TlBF₄ gives cationic derivatives [(η⁵-C₅H₅)NiL₂]BF₄ (L = 2PPh₂Me (VII); L = dppe (VIII)), whereas mononuclear complexes containing two different ligands (L₂ = PPh₃ + PCy₃ (IX)) or dinuclear [(η⁵-C₅H₅)Ni(PPh₃)]₂dppe(BF₄)₂ (X) are obtained from the reaction of III with TlBF₄ in the presence of a different ligand. Reduction of cationic complexes with Na/Hg gives very unstable nickel(I) derivatives (η⁵-C₅H₅)NiL₂, which could not be isolated purely. Similar reduction of neutral complexes under CO gives a mixture of decomposition products containing [(η⁵-C₅H₅)Ni(CO)]₂ and nickel(o) carbonyls, whereas in the presence of acetylenes, dinuclear [(η⁵-C₅H₅)Ni]₂(RCCR′) (R = R′ = Ph; R = Ph, R′ = H) are obtained.     

Chemistry of (η5-C5H5)Ru(Ph2PCH2CH2PPh2)Cl: preparation of cationic ruthenium olefin complexes

The cationic ruthenium complexes [(η⁵-C₅H₅)Ru(Ph₂PCH₂CH₂PPh₂)L]PF₆ (L=olefin, CO, pyridine or acetonitrile) have been prepared by treatment of (η⁵-C₅H₅)Ru(Ph₂PCH₂CH₂PPh₂)Cl with L and NH₄PF₆ in methanol of 20°C.     

Ligand-centred coupling of the alkynyl radical cations [Mo(CCR)(Ph2PCH2CH2PPh2)(η-C7H7)]+ (R = Ph or Bun: crystal structure of the dimeric product [Mo2(Ph2PCH2CH2PPh2)2(η-C7H7)2(μ-C4R2)][PF6]2 (R = Ph)

The radical cations [Mo(CCR)(dppe)(η-C₇H₇)]⁺ (R = Ph or Buⁿ); dppe = Ph₂PCH₂CH₂PPh₂) undergo coupling at C_β of the alkynyl ligand to afford the divinylidene-bridged, dimeric products [Mo₂(dppe)₂(η-C₇H₇)₂(μ-C₄R₂)]²⁺, characterised crystallographically for R = Ph.     

Vierkernige Clusterkomplexe vom Typ [MM′(AuPR3)2(μ‐H)(μ‐PCy2)(μ4‐PCy)(CO)6] (M,M′ = Mn,Re; R = Ph,Cy, Et): Synthese,Struktur und Topomerisierung

Tetranuclear Cluster Complexes of the Type [MM′(AuR₃)₂(μ‐H)(μ‐PCy₂)(μ₄‐PCy)(CO)₆] (M,M′ = Mn, Re; R = Ph, Cy, Et): Synthesis, Structure, and Topomerisation The dirhenium complex [Re₂(μ‐H)(μ‐PCy₂)(CO)₇(ax‐H₂PCy)] ( 1 ) reacts at room temperature in thf solution with each two equivalents of the base DBU and of ClAuPR₃ (R = Ph, Cy, Et) in a photochemical reaction process to afford the tetranuclear clusters [Re₂(AuPR₃)₂(μ‐H)(μ‐PCy₂)(μ₄‐PCy)(CO)₆] (R = Ph ( 2 ), Cy ( 3 ), Et ( 4 )) in yields of 35–48%. The homologue [Mn₂(μ‐H)(μ‐PCy₂)(CO)₇(ax‐H₂PCy)] ( 5 ) leads under the same reaction conditions to the corresponding products [Mn₂(AuPR₃)₂(μ‐H)(μ‐PCy₂)(μ₄‐PCy)(CO)₆] (R = Ph ( 6 ), Et ( 8 )). Also [MnRe(μ‐H)(μ‐PCy₂)(CO)₇(ax/eq‐H₂PCy)] ( 9 ) reacts under formation of [MnRe(AuPR₃)₂(μ‐H)(μ‐PCy₂)(μ₄‐PCy)(CO)₆] (R = Ph ( 10 ), Et ( 11 )). All new cluster complexes were identified by means of ¹H‐NMR, ³¹P‐NMR and ν(CO)‐IR spectroscopic measurements. 2 , 4 and 10 have also been characterized by single crystal X‐ray structure analyses with crystal parameters: 2 triclinic, space group P 1, a = 12.256(4) Å, b = 12.326(4) Å, c = 24.200(6) Å, α = 83.77(2)°, β = 78.43(2)°, γ = 68.76(2)°, Z = 2; 4 monoclinic, space group C2/c, a = 12.851(3) Å, b = 18.369(3) Å, c = 40.966(8) Å, β = 94.22(1)°, Z = 8; 10 triclinic, space group P 1, a = 12.083(1) Å, b = 12.185(2) Å, c = 24.017(6) Å, α = 83.49(29)°, β = 78.54(2)°, γ = 69.15(2)°, Z = 2. The trapezoid arrangement of the metal atoms in 2 and 4 show in the solid structure trans‐positioned an open and a closed Re…Au edge. In solution these edges are equivalent and, on the ³¹P NMR time scale, represent two fluxional Re–Au bonds in the course of a topomerization process. Corresponding dynamic properties were observed for the dimanganese compounds 6 and 8 but not for the related MnRe clusters 10 and 11 . 2 and 4 are the first examples of cluster compounds with a permanent Re–Au bond valence isomerization.     

Synthesis of cationic dialkylgold(III) complexes: nature of the facile reductive elimination of alkane

A series of gold(III) cations of the type cis-[CH₃)₂AuL₂]⁺ X^? where L  Ph₃, PMePh₂, PMe₂Ph, PMe₃, AsPh₃, AsPh₃, SbPh₃, $\text{1}\text{2}$H₂NCH₂CH₂NH₂, $\text{1}\text{2}$ Ph₂PCH₂CH₂-PPh₂, $\text{1}\text{2}$ Ph₂AsCH₂CH₂AsPh₂, and $\text{1}\text{2}$o-C₆H₄(AsMe₂)₂ and X  BF₄^?, PF₆^?, ClO₄^?, and F₃CSO₃^? has been prepared. In addition, the cis complexes [(CH₃)(CD₃)-Au(PPh₃)₂]F₃CSO₃, [(C₂H₅)₂Au(PPh₃)₂]F₃CSO and [(n-C₄H₉)₂Au(PPh₃)₂]F₃-CSO₃ have been synthesized. All have been characterized by PMR, Raman and infrared spectroscopy. These [R₂AuL₂]X compounds yield only ethane, butane, or octane via reductive elimination, and no disproportionation is observed. The alkane eliminations have been studied in CHCl₃, CH₃Cl₂, and CH₃COCH₃ solution as a function of temperature, concentration of the complex, and concentration of added ligand L. Elimination is fastest when L is bulky (PPh₃ > PMePh₂ > PMe₂Ph > PMe₃), decreases in the sequence SbPh₃ > AsPh₃ > PPh₃, is slow with chelating ligands, is inhibited by excess ligand, and there is small anion effect as X is varied. As R is varied, the rate of elimination decreases Bu ? Et > Me. An intramolecular dissociative mechanism is proposed which involves rapid elimination of alkane from an electron deficient dialkylgold(III) complex with nonequivalent gold—carbon bonds and produces the corresponding [AuL₂]X complex.     

Synthesis and characterization of silver(I) complexes with N‐thiophosphorylated thiobenzamide or thiourea and phosphines

A reaction of the potassium salts of RC(S)NHP(S)(OiPr)₂ (R = PhNH, HL ^I; Ph, HL ^II) with a mixture of AgNO₃ and Ph₂P(CH₂)_{1 − 3}PPh₂ or Ph₂P(C₅H₄FeC₅H₄)PPh₂ in aqueous EtOH/CH₂Cl₂ leads to [Ag₂(Ph₂PCH₂PPh₂)₂L^INO₃] ( 1 ), [Ag{Ph₂P (CH₂)₂PPh₂}L^I,II] ( 2, 6 ), [Ag{Ph₂P(CH₂)₃PPh₂}L^I,II] ( 3, 7 ), [Ag{Ph₂P(C₅H₄FeC₅H₄)PPh₂}L^I,II] ( 4, 8 ), and [Ag₂(Ph₂PCH₂PPh₂)L^II₂] ( 5 ) complexes. The structures of these compounds were investigated by ¹H and ³¹P{¹H} NMR spectroscopy and elemental analyses. It was established that the binuclear complexes 1 and 5 are luminescent in the solid state at ambient conditions. © 2010 Wiley Periodicals, Inc. Heteroatom Chem 21:386–391, 2010; View this article online at wileyonlinelibrary.com . DOI 10.1002/hc.20627     

Derivate des borols: IX. (η5-borol)metall-komplexe von ruthenium,osmium und rhodium

Dehydrogenating complexation of borolenes with carbonyls (Ru₃(CO)₁₂, Os₃(CO)₁₂), Wilkinson's catalyst (RhCl(PPh₃)₃) and related compounds (RuCl₂(PPh₃)₃, RuHCl(PPh₃)₃, OSCl₂(PPh₃)₃), and (η⁶-arene)ruthenium complexes (Ru(η-C₆H₆)(η⁴-C₆H₈), [Ru(η-C₆H₆)Cl₂]₂, [Ru(η-C₆-Me₆)Cl₂]₂) leads to the (η⁵-borole)metal complexes of Ru, Os, and Rh. Inter alia, the preparation of the complexes Ru(CO)₃(η⁵-C₄H₄BF) (R = Ph, OMe, Me), Os(CO)₃L (L = η⁵-C₄H₄BPh), MHClL(PPh₃)₂ (M = Ru, Os), RhClL(PPh₃)₂, and RuL(η-C₆R₆) (R = H, Me) is described. The structures of RuHClL(PPh₃)₂ and RhClL(PPh₃)₂ have been determined by X-ray diffraction analysis.