20545-30-6Relevant academic research and scientific papers
An economical small-scale synthesis of the μ-nitridobis(triphenylphosphonium) cation, +
Lalor, F. J.,Chaona, S.
, p. 163 - 166 (1988)
Substitution of bromine for chlorine in the literature procedure for the preparation of the μ-nitridobis(triphenylphosphonium> cation allows the scale to be considerably reduced without serious loss of yield, and effects a significant reduction in the ove
Stepwise cyclopalladation of 2-phenacylthiopyridine to give C,C,N-pincer complexes
Chicote, Mara-Teresa,Rubio, Concepcin,Bautista, Delia,Vicente, Jos
, p. 15170 - 15182 (2014)
Orthopalladation of the phenyl ring in the cyclopalladated complex [Pd{C,N-pyl-SCHC(O)Ph}(μ-X)]2 (pyl = 2-pyridyl, X = Cl; 1·Cl) occurs upon reacting it with AgOAc (1+:+2) in MeCN to give the pincer complex [Pd{C,C,N-pyl-SCHC(O)C6H4-2}(NCMe)] (2). The nature of the base and X plays a key role because palladation neither occurs with other bases nor when AgOAc is the base and X is Br, in which case 1·OAc is obtained. In addition, complex 2 is not obtained upon refluxing 1·OAc in MeCN. Complex 2 affords complexes [Pd{C,C,N,S-pyl-SCHC(O)C6H4-2}]n, [Pd{C,C,N-pyl-SCHC(O)C6H4-2}L] (L = PPh3, tBuNC, XyNC) or Me4N[Pd{C,C,N-pyl-SCHC(O)C6H4-2}Cl] upon acetonitrile loss, or its replacement by neutral or anionic ligands, respectively. Some such complexes act as metallaligands towards AgClO4 or [PdCl2(NCPh)2] giving rise to heterodinuclear [{Pd{C,C,N-pyl-SCHC(O)C6H4-2}(PPh3)}{Ag(PPh3)}]ClO4 or homodinuclear [{Pd{C,C,N-pyl-SCHC(O)C6H4-2}(Cl)}{Pd(μ-Cl)}]2, [{Pd{C,C,N-pyl-SCHC(O)C6H4-2}(Cl)}{Pd(Cl)(PPh3}] complexes. Some derivatives of complexes 1 were also obtained. This journal is
PHOSPHONIUM AZA-YLDIID AS REAGENT FOR ONE-POT SYNTHESIS OF PHOSPHINIMINES WITH FUNCTIONAL N-SUBSTITUENTS.
Cristeau, Henri-Jean,Manginot, Eric,Torreilles, Eliane
, p. 347 - 350 (2007/10/02)
A new procedure for the one-pot synthesis of phosphinimines with functional N-substituents using the alkylation of phosphonium aza-yldiid 1 with α-bromo esters or the direct introduction of phosphorus and sulfur groups.
Substitution Reactions toward 2-Nitrobenzyl Pseudohalides. The Crystal Structure of 2-Nitrobenzyl Tellurocyanate
Grung, Knut Eric,Roemming, Christian,Songstad, Jon
, p. 518 - 526 (2007/10/02)
The reactions between 2-nitrobenzyl pseudohalides, 2-NO2-PhCH2XCN, and pseudohalide ions, NCX- (X = S, Se or Te) have been studied kinetically in acetonitrile at 25.0 deg C.The reactions proceed through nucleophilic attack at the methylene carbon atom, forming exclusively the exchange products.The average nucleophilicity order, NCTe- >> NCSe- > NCS-, and the average leaving group order, NCTe- >/= NCSe- >/= NCS-, lead to a carbon basicity order NCTe- > NCSe- >/= NCS-, which is confirmed with equilibrium studies.A crystal structure determination of 2-nitrobenzyl tellurocyanate at ca. 135 deg C has revealed that the TeCN group is syn-clinal (gauche) to the C(CH2)-C(Ar) bond with a torsion angle of -48.5(5) deg.The TeCC plane forms an angle of 103.4(5) deg with the phenyl ring plane.In this conformation the steric influence of the 2-NO2 group in substitution reactions at the methylene carbon atom will be negligible except for bulky nucleophiles.The tellurium atom forms two fairly strong intermolecular bonds to nitrogen atoms from neighbouring tellurocyanate groups, viz. 2.889(6) Angstroem trans to the cyano group and 3.382(6) Angstroem trans to the methylene group.In the crystalline state the compound may be considered both as a tellurium(II) complex and as an organic pseudohalide.No intermolecular tellurium-oxygen contacts could be observed.
Thiolate, Thioether, and Thiol Derivatives of Iron(0) Carbonyls
Liaw, Wen-Feng,Kim, Christine,Darensbourg, Marcetta Y.,Rheingold, Arnold L.
, p. 3591 - 3597 (2007/10/02)
A new series of anionic complexes of iron tetracarbonyl monofunctionalized with the ligand ->,-> (R = Ph, Et, Me, H), have been synthesized and characterized.The compound was formed in the reaction of and PhSSPh.The -> anion was characterized by X-ray diffraction as its +> salt and found to be a typical trigonal-bipyramidal complex in which the phenylthiolate ligand occupies an axial position with a Fe-S bond distance of 2.332(5) Angstroem and Fe-S-C(Ph) = 111.3(6) deg.The salt crystallized inthe orthorhombic space group Pbc21, with a = 9.529(4) Angstroem, b = 21.493(9) Angstroem, c = 20.185(9) Angstroem, V = 4134(3) Angstroem3, and Z = 2.Other members of the series of complexes, ->, were best obtained by ligand exchange of -> and the labile thioether complex (PhSMe)Fe(CO)4.The latter was produced from the low-temperature alkylation of the ->.Protonation of the thiolates (R = Ph, Et, Me, H) ultimately leads to formation of H2 and Fe2(μ-SR)2(CO)6; however, the intermediate thiol, (RSH)Fe(CO)4, could be observed at -78 to -40 deg C for R = Et, Me.The PhSH and HSH derivatives were unstable even at -78 deg C.
Transition-metal trihalomethyl complexes as cluster-building reagents: Preparation and X-ray crystal structure of [PPN][MnCo2(CO)9(μ3-CCO)]
Crespi, Ann M.,Went, Michael J.,Sunshine, Steven S.,Shriver, Duward F.
, p. 214 - 218 (2008/10/08)
A new mixed-metal ketenylidene complex, [PPN][MnCo2(CO)9(μ3-CCO)] (1) (PPN+ = bis(triphenylphosphine)nitrogen(1+)), has been prepared from trihalomethyl manganese complexes, Mn(CO)5(CX3) (X = Cl or Br), in combination with [PPN][Co(CO)4]. Attempts to extend this technique to other trihalomethyl complexes and metal carbonyl anions did not yield any new cluster products. Instead, these reactions were characterized by electron-transfer chemistry, which resulted in oxidation of the anions. Crystal data for 1: triclinic space group P1; a = 14.859 (4) A?, b = 9.209 (1) A?, c = 16.701 (3) A?, a = 90.08 (2)°, β = 102.79 (2)°, γ = 89.99 (2)° Z = 2. Protonation of 1 leads to the new mixed-metal methylidyne MnCo2(CO)10(μ3-CH) (2).
