603-35-0Relevant articles and documents
Synthesis and characterization of the [Ni6Ge13(CO) 5]4- and [Ge9Ni2(PPh 3)]2- Zintl ion clusters
Esenturk, Emren N.,Fettinger, James,Eichhorn, Bryan
, p. 521 - 529 (2006)
Reactions between K4Ge9, Ni(CO)2(PPh 3)2, and 2,2,2-crypt in ethylenediamine solutions give two different products depending on reaction conditions. The [Ni6Ge 13(CO)5]4- ion (1) is formed at low temperatures (～40°C) and short reaction times whereas the [Ge 9Ni2(PPh3)]2- ion (2) forms at higher temperatures (～118°C). Both complexes were isolated as [K(2,2,2-crypt)]+ salts and characterized by single-crystal X-ray diffraction, electrospray mass spectrometry (ESI-MS) and NMR studies ( 13C and 31P). 1 has a hypo-closo cluster electron count (Wades Rules) and adopts an interpenetrating biicosahedral structure with 17 vertices and 2 interstitials, which is unique in transition metal Zintl ion clusters. 2 also has a hypo-closo cluster electron count but displays an open, nido-like 10-vertex structure with a Ni interstitial. The composition of 2 was established through ESI-MS studies and corrects an earlier report that characterized the cluster as [Ge10Ni(PPh3)]2- with an interstitial Ge.
Cluster-Mediated Conversion of Diphenylacetylene into α-Phenylcinnamaldehyde. Construction of a Catalytic Hydroformylation Cycle Based on Isolated Intermediates
Nombel, Paul,Lugan, No?l,Donnadieu, Bruno,Lavigne, Guy
, p. 187 - 196 (1999)
The present paper deals with a rational attempt to achieve the hydroformylation of diphenylacetylene onto a hydrido triruthenium cluster complex incorporating the 2-(methylamino)pyridyl group (abbreviation: MeNpy) as a hemilabile ancillary ligand [note: in all species discussed below, the bridgehead μ2-N atom is linked to the centers labeled as Ru(1) and Ru(2), whereas the pyridyl nitrogen is bound to Ru(3)]. The complex Ru3(μ-H)(μ-MeNpy)-(CO)9 (1) is shown to react cleanly with diphenylacetylene to give the alkenyl complex Ru3-(μ-MeNpy)(μ-PhC=CHPh)(CO)8 (2), the structure of which is reported. The reaction of 2 with 1 equiv of PPh3 proceeds to completion within less than 3 min at 25 °C, giving two propenoyl complexes, namely, Ru3(μ-MeNpy)(μ-O=C-PhC=CHPh)(PPh3)(CO)7 (3) (48% yield) and Ru3(μ-MeNpy)(μ-O=C-PhC=CHPh)(PPh3) 2(CO)6 (4) (19% yield), both fully characterized by spectroscopic methods and X-ray analysis. Complex 3 is an adduct of 2 with PPh3. The incorporation of the phosphine has caused a migratory CO insertion of the alkenyl group. The phosphine occupies an equatorial coordination site on Ru(1), in cis position relative to the nitrogen atom of the amido bridge. The newly formed propenoyl group occupies an equatorial bridging position across the Ru(1)-Ru(3) edge, with the acyl oxygen bound to Ru(1), in cis position relative to both the bridgehead nitrogen atom and the phosphine. The molecular structure of the second propenoyl compound, Ru3(μ-MeNpy)(μ-O=C-PhC=CHPh)-(PPh3) 2(CO)6 (4), is formally derived from the previous one, 3, by a simple substitution of an equatorial CO of Ru(2) by PPh3. The use of a 2-fold amount of phosphine for the above reaction modifies only slightly the relative abundance of 3 (30%) and 4 (44%). This indicates that 3 is not the kinetic product of the reaction between 2 and a phosphine. Further reaction of 4b with CO induces loss of one PPh3 and incorporation of two CO ligands. This produces the open 50e cluster Ru3(μ-MeNpy)(μ-O=C-PhC=CHPh)(PPh3)(CO)8 (5), in which the bridging propenoyl group now spans the open edge Ru(1)-Ru(2) (the remaining phosphine occupies an equatorial site cis to the acyl oxygen). Treatment of 2b with CO (1 atm, 25 °C, 20 min) also promotes migratory CO insertion, giving the 50e propenoyl complex Ru3(μ-MeNpy)(μ-O=C-PhC=CHPh)(CO)9 (6b), whose structure has been determined. The propenoyl group spans the open edge Ru(1)-Ru(2). Although stable in CO-saturated solutions under CO atmosphere, the complex reverts rapidly to 2 within 30 s under inert atmosphere. Treatment of 6 with CO/H2 gas mixtures under ambient conditions produces α-phenylcinnamaldehyde with concomitant recovery of 1, showing that the hydroformylation of diphenylacetylene can be achieved in a stepwise manner through the cyclic reaction sequence 1 → 2 → 6 → 1. Under nonoptimized catalytic conditions, the amount of α-phenylcinnamaldehyde obtained corresponds to about eight cycles. The metal-containing species recovered in the reactor through the catalytic runs is isolated and formulated as the bimetallic carboxamido complex [Ru{-C(O)-MeNpy}(CO)3]2 (7). Thus, it appears that deactivation of the system has taken place via CO insertion into the metal-amide bond.
Reactions of but-2-yne-1,4-diylbis(triphenylphosphonium) dihalides with SH- and NH-nucleophiles
Bichakhchyan
, p. 1041 - 1045 (2016)
But-2-yne-1,4-diylbis(triphenylphosphonium) diiodide reacts with 2-sulfanylethan-1-ol in the presence of triethylamine to form a 1 : 1 adduct. Under similar conditions, ethane-, butane- and 2-methylbutane- 1-thiols form [4-(alkylsulfanyl)buta-1,3-dien-1-yl]triphenylphosphonium iodides, probably via β-cleavage of the original salt involving vinylethynyl intermediate. Features of the reaction of but-2-ynebisphosphonium salt with 3,5-dimethylpyrazole, hydrazine and its derivatives have been studied.
The behavior of 3,3-diphenylindan-1,2-dione towards phosphonium ylides
Osman, Fayez H.,El-Samahy, Fatma A.
, p. 545 - 552 (2007)
The reaction of alkoxycarbonyl- and cyanomethylene(triphenyl)phosphoranes with 3,3-diphenylindan-1,2-dione in dry benzene at room temperature for about 5∈h led to the formation of a mixture of (E)- and (Z)-diastereomers. On the other hand, treatment of the dione with acetylmethylene(triphenyl)phosphorane afforded a mixture of (E)-3,3-diphenyl-1-(2-oxo-2-methylethylidene)indan-2-one and unexpected product (E)-3-(3,3-diphenyl-2-oxoindan-1-ylidene)-4-(triphenyl- λ5-phosphanylidene)hexane-2,5-dione, whereas with benzoylmethylene(triphenyl)phosphorane gave a mixture of (E)-3,3-diphenyl-1-(2- oxo-2-phenylethylidene)indan-2-one, [(2R *,3S *)-3-benzoyl-8,8- diphenyl-3,8-dihydro-2H-indeno{2,1-b}furan-2-yl]phenylmethanone and 1,4-diphenyl-2-(3,3-diphenyl-2-hydroxy-3H-inden-1-yl)but-2-ene-1,4-dione. The reaction mechanisms are considered and structural assignments of the new compounds are based on spectroscopic evidence. The molecular structures of the two diastereomers and the unexpected product were elucidated by X-ray crystallography. Springer-Verlag 2007.
Phosphane-functionalized heavier tetrylenes: Synthesis of silylene- And germylene-decorated phosphanes and their reactions with Group 10 metal complexes
Cabeza, Javier A.,García-álvarez, Pablo,Laglera-Gándara, Carlos J.,Pérez-Carre?o, Enrique
, p. 8331 - 8339 (2020)
The stable phosphane-functionalized heavier tetrylenes E(tBu2bzam)pyrmPtBu2 (E = Si (1Si), Ge (1Ge); tBu2bzam = N,N′-ditertbutylbenzamidinate; HpyrmPtBu2 = ditertbutyl(2-pyrrolylmethyl)phosphane) have been prepared by reacting the amidinatotetrylenes E(tB
Synthesis and structural characterization of isomeric 'lantern-shaped' platinum(III) complexes of formula [Pt2(PPh3)X{N(H)C(R)O}4](NO3) 2 (X=PPh3, H2O)
Bandoli, Giuliano,Dolmella, Alessandro,Intini, Francesco P.,Pacifico, Concetta,Natile, Giovanni
, p. 143 - 150 (2003)
The platinum(III) lantern type complexes [Pt2(PPh3)2{N(H)C(R)O}4](NO 3)2 [R=Me (1), But (2)], and [Pt2(H2O)(PPh3){N(H)C(But)O} 4](NO3)2 (3) were synthesized and characterized by 1H NMR and X-ray crystallography (2 and 3). The compounds can give rise to formation of isomers differing for the sets of equatorial donor atoms around each platinum, N3O/NO3 or N2O2, and, in the case of N2O2, for the cis or trans geometry. The effect of the anion upon the chemical shifts of NH protons was studied for NO3-, BF4-, and ClO4-. The stability of phosphine axial ligands in the complexes N3O/NO3-[Pt2(PPh3) 2{N(H)C(R)O}4](NO3)2 as a function of the set of donor atoms was also studied. The complex N3O/NO3-3 is the fist non-symmetric lantern-type platinum dimer to be characterized by X-ray diffraction. Comparison of the platinum/axial ligand bond distances in different complexes of this type allows to conclude that two factors contribute to the lengthening of axial bonds: the strong trans labilizing effect of the intermetallic bond and the trans-influence of the axial ligand on the second platinum unit.
TMSCl-promoted electroreduction of triphenylphosphine oxide to triphenylphosphine
Tanaka, Hideo,Yano, Tomotake,Kobayashi, Kazuma,Kamenoue, Syogo,Kuroboshi, Manabu,Kawakubo, Hiromu
, p. 582 - 584 (2011)
Direct reductive transformation of triphenylphosphine oxide to triphenylphosphine was performed successfully by electrolysis with TMSCl in an acetonitrile/BuBr/(Zn anode)-(Pt cathode)/undivided cell/constant current electrolysis system. A plausible ECEC mechanism involving the formation of silylated phosphorus radical is proposed. Georg Thieme Verlag Stuttgart New York.
Triphenylphosphonium Bromide: A Convenient and Quantitative Source of Gaseous Hydrogen Bromide
Hercouet, A.,Corre, M. Le
, p. 157 - 158 (1988)
Thermolysis of triphenylphosphonium bromide in refluxing xylene provides quantitative yield of anhydrous hydrogen bromide.
Electroreduction of triphenylphosphine dichloride and the efficient one-pot reductive conversion of phosphine oxide to triphenylphosphine
Yano, Tomotake,Kuroboshi, Manabu,Tanaka, Hideo
, p. 698 - 701 (2010)
Electroreduction of triphenylphosphine dichloride in acetonitrile was performed successfully in an undivided cell fitted with an aluminium sacrificial anode and a platinum cathode. Further, the one-pot transformation of triphenylphosphine oxide to triphenylphosphine was achieved successfully by the treatment of triphenylphosphine oxide in acetonitrile with oxalyl chloride and subsequent electrochemical reduction.
DISSOCIATION OF THE (4H-FLAVEN-4-YL)TRIPHENYLPHOSPHONIUM CATION IN ACETONITRILE
Bumber, A. A.,Kisarova, L. I.,Arzumanyants, E. A.,Abaev, V. T.,Palui, G. A.
, p. 868 - 871 (1989)
The thermodynamic and kinetic parameters of the reversible dissociation of (4H-flaven-4-yl)triphenylphosphonium perchlorate in acetonitrile were determined.
