603-35-0Relevant articles and documents
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Wunsch et al.
, p. 33,35,36 (1969)
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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.
Benedikt, M.,Schloegl, K.
, (1978)
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.
Eaton,Suart
, p. 4170 (1968)
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.
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Arai,Halpern
, p. 1571 (1971)
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Augustine, R. L.,Peppen, J. F. van
, (1970)
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.
Nonterminating alternating copolymerization of ethene with carbon monoxide and the synthesis of graft polymers with alt-ethene-carbon monoxide blocks
Kacker, Smita,Sen, Ayusman
, p. 10591 - 10592 (1995)
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Synthesis of ruthenium phenylindenylidene, carbyne, allenylidene and vinylmethylidene complexes from (PPh3)3-4RuCl2: A mechanistic and structural investigation
Shaffer, Erika A.,Chen, Chun-Long,Beatty, Alicia M.,Valente, Edward J.,Schanz, Hans-J?rg
, p. 5221 - 5233 (2007)
The reaction of (Ph3P)3RuCl2 with 1,1-diphenyl-2-propyn-1-ol was investigated in various solvents. The reaction in thf under reflux is reported to produce the (PPh3)2Cl2Ru(3-phenylindenylidene) complex (3) which has undergone rearrangement of the allenylidene C3-spine. We have improved the reliability of the reported synthesis by adding acetyl chloride which converts the formed water of the reaction and thus increases the acidity of the reaction solution. Without the additive, we observed the exclusive formation of an intermediate of the transformation and identified it as dinuclear (PPh3)2ClRu(μ-Cl)3(PPh3)2Ru{double bond, long}C{double bond, long}C{double bond, long}CPh2 complex (5). The reaction of (Ph3P)3-4RuCl2 with 1,1-diphenyl-2-propyn-1-ol in CH2Cl2 or C2H4Cl2 under reflux in the presence of excess conc. aqueous HCl afforded the new, neutral (PPh3)2Cl3Ru{triple bond, long}C-CH{double bond, long}CPh2 carbyne complex (7), an HCl adduct of previously elusive (PPh3)2Cl2Ru{double bond, long}C{double bond, long}C{double bond, long}CPh2 complex 6 in high yields. In contrast to the formation of complex 3, the reaction in a non-coordinating solvent did not afford the rearrangement of the allenylidene C3-spine. Complex 7 was converted into complex 3 in thf under reflux under loss of a molecule HCl. Complex 7 was converted with triethylamine under loss of HCl to complex 6. Pentacoordinate complex 6 was crystallized in the presence of O-donor ligands (EtOH, MeOH and H2O) to give hexacoordinate (PPh3)2Cl2(ROH)Ru{double bond, long}C{double bond, long}C{double bond, long}CPh2 (R = H, CH3, C2H5) complexes (9)-(11) with the O-donor coordinating in trans-position to the allenylidene moiety. The reaction of complex 7 with 2 equiv. of 4-(N,N-dimethylamino)pyridine (DMAP) gave hexacoordinate (PPh3)2Cl2(DMAP)Ru{double bond, long}C{double bond, long}C{double bond, long}CPh2complex (12) with one molecule DMAP also coordinating in trans-position to the allenylidene group. Methanol and acetic acid in the absence of strong bases afforded the Fischer-carbene complexes (PPh3)2Cl2Ru{double bond, long}C(OCH3)-CH{double bond, long}CPh2 (14) and (PPh3)2Cl2Ru{double bond, long}C(OAc)-CH{double bond, long}CPh2 (15) where the nucleophile added to the α-carbon atom. The structures of complexes 5, 7, 9-11, 14, and 15 were solved via X-ray crystallography.
Mono-and dihydrophosphoranes and dihydrophosphoranates as intermediates in the reaction of phosphonium salts with LiAiH4
Donoghue, Neil,Gallagher, Michael J.
, p. 169 - 173 (1997)
Reduction of tetraphenylphosphonium bromide with LiAlH(D)4 at room temperature affords first the monohydrophosphorane Ph4PH, then the dihydrophosphoranate anion [Ph4PH2]- which decomposes to the dihydrophosphorane Ph3PH2, all of which are identified by 31PNMR. Reductions of other phosphonium salts appear to follow a similar path. At elevated temperatures none of these intermediates is observed and attempted isolation leads to extensive decomposition.
Photochemical transformation of chlorobenzenes and white phosphorus into arylphosphines and phosphonium salts
Gschwind, Ruth M.,Mende, Michael,Scott, Daniel J.,Streitferdt, Verena,Till, Marion,Wolf, Robert
supporting information, p. 1100 - 1103 (2022/02/03)
Chlorobenzenes are important starting materials for the preparation of commercially valuable triarylphosphines and tetraarylphosphonium salts, but their use for the direct arylation of elemental phosphorus has been elusive. Here we describe a simple photochemical route toward such products. UV-LED irradiation (365 nm) of chlorobenzenes, white phosphorus (P4) and the organic superphotoreductant tetrakis(dimethylamino)ethylene (TDAE) affords the desired arylphosphorus compounds in a single reaction step.
Coordination Chemistry of Borane in Solution: Application to a STING Agonist
Lemaire, Sébastien,Zhdanko, Alexander,van der Worp, Boris A.
, (2022/04/09)
Equilibrium constants were determined for ligand exchange reactions of borane complexes with various oxygen, sulfur, nitrogen, and phosphorus nucleophiles in solution, and a binding affinity scale was built spanning a range of 12 orders of magnitude. While the Keq are minimally dependent on the solvent, the rate of ligand exchange varies significantly. The fastest and slowest rates were observed in THF and CDCl3, respectively. Moreover, the ligand exchange rate differs in a very broad range depending on stability of the starting complex. Binding of BH3 was found to be much more sensitive to steric factors than protonation. Comparing nitrogen bases having equal steric properties, a linear correlation of BH3 binding affinity vs. Br?nsted acidity was found. This correlation can be used to quickly estimate the BH3 binding affinity of a substrate if pKa is known. Kinetic studies suggest the ligand exchange to occur as a bimolecular SN2 reaction unless other nucleophilic species were present in the reaction mixture.
Selective P-C bond cleavage of tertiary phosphine boranes by sodium
Zhang, Jian-Qiu,Ye, Jing-Jing,Han, Li-Biao
, p. 961 - 964 (2021/07/19)
Herein reported is the facial modification of tertiary phosphine boranes R3PBH3 by selective cleaving the P-Ph bond by sodium in which the phosphide borohydride R2PNa(BH3) is quantitatively generated and could be easily quenched by electrophiles to furnish a series of new phosphine boranes in high yields.