141547-34-4Relevant academic research and scientific papers
Molybdenum dinitrogen complexes facially coordinated by linear tridentate PEP ligands (E = N or P): Impact of the central e donor in: Trans -position to N2
Hinrichsen, Svea,Schnoor, Ann-Christin,Grund, Katharina,Fl?ser, Benedikt,Schlimm, Alexander,N?ther, Christian,Krahmer, Jan,Tuczek, Felix
, p. 14801 - 14813 (2016)
The syntheses of molybdenum dinitrogen complexes supported by the tridentate PEP ligands (E = N, P) prPP(Ph)P = (Ph2PCH2CH2CH2)2P(Ph), prPPHP = (Ph2PCH2CH2CH2)2PH, PN(Ph)P = (Ph2PCH2CH2)2N(Ph) and prPN(Ph)P = (Ph2PCH2CH2CH2)2N(Ph) are reported. Together with the coligand dmpm = (CH3)2PCH2P(CH3)2 dinitrogen complexes of the type [Mo(N2)(PEP)(dmpm)] are formed. The new systems are characterized by IR and NMR spectroscopy and compared with the literature-known complex [Mo(N2)(dpepp)(dmpm)] (1) (dpepp = PhP(CH2CH2PPh2)2). The consequences of the substitution of the central P-donor of dpepp by N and the replacement of its C2 by C3 linkages as well as the exchange of the EPh by an EH function are investigated with respect to the stability of the corresponding N2-complexes. Importantly, the activation of the N2 ligand drastically increases upon replacing the trans-phosphine with a trans-amine donor.
Synthesis and structure of dinuclear silver complexes of N,N-bis(2-(diphenylphosphanyl)ethyl)phenylamine
Besenyei, Gábor,Szalontai, Gábor,Párkányi, László
, p. 97 - 106 (2017)
N,N-Bis(2-(diphenylphosphanyl)ethyl)phenylamine, (PNPhP), and AgX compounds (X?=?OTf, Cl, Br, I) form dimeric complexes of general formula [Ag2X2(PNPhP)2], 1–4, in which, as revealed by crystallographic investigations, the two phosphorus donors are bound to different metal centers but the central N-donor remains unbound. NMR studies performed on solutions of any 1:1 mixtures of 2–4 demonstrated that these complexes retain their dimeric structure in solution. To the contrary, a monomer/dimer equilibrium strongly shifted toward dimerization was observed in the solutions of 1. The distribution of the dimeric species in the halide1/halide2mixtures compared to that in the OTf/halide systems is remarkably different and reflects the preference of the Ag/halide interaction over the Ag/OTf coordination. Based on the interplay of the AgP2planes, the known [Ag2(μ-X)2(μ-Ph2PYPPh2)2] complexes can be arranged into four well-discernible groups (Y stands for a 4–6-membered linkage).
Synthesis, characterization and theoretical investigations of molybdenum carbonyl complexes with phosphorus/nitrogen/phosphorus ligand as bidentate and tridentate modes
Goren Keskin, Seyma,Stanley, Julie M.,Cowley, Alan H.
, p. 206 - 217 (2017)
Carbonyl complexes of molybdenum with the phosphorus/nitrogen/phosphorus ligand, PNP-Mo(CO)n, where n = 3, 4 and PNP is N,N-bis[2-(diphenylphosphino)ethyl]phenylamine have been synthesized and characterized by 1H, 31P{1H} NMR, IR (ATR and solution state), Raman, X-ray diffraction, MS and elemental analysis. DFT calculations of the complexes were also performed. The PNP-Mo(CO)4 complex in which the binding mode is bidentate cis-phosphine and, facial and meridional isomers of PNP-Mo(CO)3 in which the binding mode is tridentate were obtained. The facial isomer and the tetracarbonyl complexes were successfully synthesized and purified; however, it was not possible to isolate the meridional isomer. Only a few crystals of the meridional isomer were detected and used for X-ray analysis. When the facial isomer was dissolved in CH2Cl2 or in THF, it was found to undergo decomposition thereby generating the tetracarbonyl complex, meridional isomer, Mo(0) as a dark precipitate along with some facial isomer that was left intact in solution. The reason that the facial isomer was the preferred structure with respect to the meridional isomer was also investigated.
Dual coordination modes of ethylene-linked NP2 ligands in cobalt(II) and nickel(II) iodides
Dong, Qingchen,Rose, Michael J.,Wong, Wai-Yeung,Gray, Harry B.
experimental part, p. 10213 - 10224 (2011/12/01)
Here we report the syntheses and crystal structures of a series of cobalt(II) and nickel(II) complexes derived from RNP2 ligands (where R = OMeBz, HBz, BrBz, Ph) bearing ethylene linkers between a single N and two P donors. The CoII complexes generally adopt a tetrahedral configuration of general formula [(NP2)Co(I) 2], wherein the two phosphorus donors are bound to the metal center but the central N-donor remains unbound. We have found one case of structural isomerism within a single crystal structure. The CoII complex derived from BzNP2 displays dual coordination modes: one in the tetrahedral complex [(BzNP2)Co(I)2]; and the other in a square pyramidal variant, [(BzNP2)Co(I)2]. In contrast, the NiII complexes adopt a square planar geometry in which the P(Et)N(Et)P donors in the ligand backbone are coordinated to the metal center, resulting in cationic species of formula [(RNP2)Ni(I)]+ with iodide as counterion. All NiII complexes exhibit sharp 1H and 31P spectra in the diamagnetic region. The Co II complexes are high-spin (S = 3/2) in the solid state as determined by SQUID measurements from 4 to 300 K. Solution electron paramagnetic resonance (EPR) experiments reveal a high-spin/low-spin CoII equilibrium that is dependent on solvent and ligand substituent.
Synthesis of new rhodium complexes with a hemilabile nitrogen-containing bis(phosphinite) or bis(phosphine) ligand. Application to hydroformylation of styrene
Kostas, Ioannis D.
, p. 221 - 226 (2007/10/03)
Two new cationic rhodium(I) complexes with a hemilabile nitrogen-containing bis(phosphinite) or bis(phosphine) ligand have been prepared. 31P-NMR studies provide evidence that the ligands are coordinated to the metal in P,P-bidentate mode, wher
