155932-48-2Relevant academic research and scientific papers
Bonding and Activation of N2 in Molybdenum(0) Complexes Supported by Tripod Ligands with Phospholane End Groups
Pfeil, Mareike,Engesser, Tobias A.,Krahmer, Jan,N?ther, Christian,Tuczek, Felix
, p. 1778 - 1788 (2021)
Tripod ligands with a neopentyl backbone and one (trpd-1 pln), two (trpd-2 pln) or three (trpd-3 pln) phospholane end groups are synthesized and used for the synthesis of MoX3 (X=Cl, Br, I) complexes supported by these ligands. NaxHg
Molybdenum(0) Dinitrogen Complexes Supported by Pentadentate Tetrapodal Phosphine Ligands: Structure, Synthesis, and Reactivity toward Acids
Hinrichsen, Svea,Kindjajev, Andrei,Adomeit, Sven,Krahmer, Jan,N?ther, Christian,Tuczek, Felix
, p. 8712 - 8722 (2016)
The syntheses of two pentadentate tetrapodal phosphine (pentaPodP) ligands, P2PhPP2Ph and P2MePP2Ph, are reported, which derive from the fusion of a tripod and a trident ligand. Reaction of the ligand P2PhPP2Ph with [MoCl3(THF)3] followed by an amalgam reduction under N2 does not lead to well-defined products. The same reactions performed with the ligand P2MePP2Ph afford the mononuclear molybdenum dinitrogen complex [MoN2(P2MePP2Ph)]. Because of the unprecedented topology of the pentaphosphine ligand, the Mo-P bond to the phosphine in the trans position to N2 is significantly shortened, explaining the very strong activation of the dinitrogen ligand (νNN = 1929 cm-1). The reactivity of this complex toward acids is investigated.
Spectroscopic and reactivity differences in metal complexes derived from sulfur containing Triphos homologs
Petuker,Gerschel,Piontek,Ritterskamp,Wittkamp,Iffland,Miller,Van Gastel,Apfel
, p. 13251 - 13262 (2017/10/16)
Herein, we report a simplified method for the synthesis of Triphos homologs H3CC(CH2X)n(CH2Y)3-n (X = SPh, Y = PPh2, n = 0-3). The multidentate compounds were tested for their potential to coordinate metals such as Ni, Fe, and Mo under the same experimental conditions. Cyclic voltammetry, spectroelectrochemical IR investigations as well as DFT calculations were used to examine the electronic alterations in a series of [{H3CC(CH2X)n(CH2Y)3-n}Mo(CO)3] complexes and to evaluate their potential to open coordination sites or to release CO upon oxidation or in the presence of different solvents. In addition, we demonstrate that the catalytic hydrosilylation of N,N-dimethylbenzamide to N,N-dimethylbenzylamine is influenced by the applied tripodal ligand. Our investigations show the high potential of such manipulations to selectively alter the dynamics of the binding properties of Triphos-metal complexes and their reactivity.
Chirale tripodliganden mit phosphor- uni schwefeldonoren. synthese und komplexchemie chiral tripod ligands with phosphorus and sulfur donors. Synthesis and complex chemistry
Reinhard, Gunther,Soltek, Rainer,Huttner, Gottfried,Barth, Annette,Walter, Olaf,Zsolnai, Laszlo
, p. 97 - 108 (2007/10/02)
Neopentane based tripod licands CH3C(CH2X)(CH2Y)(CH2Z) with mixed donor groups X,Y,Z (PR2, SR, SH) are accessible via two different strategies. The functionalized thietane CH3(CH2X)tCH2SCH2 allows stepwise introduction of P or S donors by substitution of the mesylate function and subsequent nucleophilic cleavage of the thietane ring. Tripod ligands 5 [CH3C(CH2X)(CH2Y)(CH2Z)j with up to three different donor groups (X = SH; Y = PPh2; Z = P;4-Tol)2, SCH2Ph, PPh2 are thus available. As an alternative the neopentano aerivatives 8 [CH3C;CH2X)(CH2Y)(CH2C1)] which are easily assessible from CH3C(CH2OSO2Me)(CH2BrJ(CH 2Cl) (7) by stepwise substitution with phosphides LiPAr2 (Ar = aryl) may be transiormed to 9 [CH3C(CH2X)(CH2Y)(CH2SBzl)]. Under controlled condi-tions the S-benzyl bond of 9 is cleaved reductively without concomitant cleavage of P-Ar bonds. Ligand 5a [CH3C(CH2PPh.)2(CH2SH)] reacts with Ni;BF4J26 H2O to yield the dinuclear species [(CH3C(CH2PPh2)2(CH 2S)Ni)2]2+ (10). The two ligands are bonded in an equivalent way with each of the two nickel centers interacting with one of the two phosphane functions of the ligand; the thiolate functions form (i2-SR bridges between the two nickel atoms. The SCH2 group at the four-membered S2Ni2 ring are in mutual cis position with the four-membered ring bent along the sulfur-sulfur axis by 70°. The internal strain in 10 is analyzed by comparing its structure with the ones of [(CH3C(CH2PPh2)2NiSPh) 2j2+ (11) and i(CH3C(CH2OH)(CH2PPh2)2. NiOH}2]2+ (12). VCK Venagsgcsci.schaf: mbH, 1996.
Eine einfache Synthese von Tripod-Liganden H3CC(CH2PAr2)3: Anwendungsbreite und Komplexchemie
Muth, A.,Walter, O.,Huttner, G.,Asam, A.,Zsolnai, L.,Emmerich, Ch.
, p. 149 - 164 (2007/10/02)
The reaction of 1,1,1-tris(chlormethyl)ethane H3CC(CH2Cl)3 with Ar2PH in DMSO as the solvent using KOH/H2O as the base gives good yields of tripod ligands H3CC(CH2PAr2)3, 2.Using Ph2PH as the phosphine component, it is shown that the chloride substituents
