28425-04-9Relevant academic research and scientific papers
Self-assembly of metal-organic hybrid nanoscopic rectangles
Ghosh, Sushobhan,Mukherjee, Partha Sarathi
, p. 2542 - 2546 (2007)
The combination of an amide containing a linear ligand (L1) and an organometallic molecular "clip" (clip-1) leads to the self-assembly of a Pt4 nanoscopic framework representing the first example of a Pt-based molecular rectangle (rectangle-1)
1,3-Bis(α-aminoisopropyl)benzene, meta-C6H4(CMe2NH2)2: An N,N-bridging and N,C,N-cyclometalating ligand
Dahlenburg, Lutz,Treffert, Harald,Heinemann, Frank W.
, p. 1311 - 1318 (2008)
Saponification of the bis(carbamic acid ester) 1,3-C6H4(CMe2NHCO2Me)2 (1), made by the addition of methanol to commercial 1,3-C6H4(CMe2NCO)2, yielded the me
3-Dimethylaminopropyl chalcogenolate complexes of palladium(II): Syntheses and characterization, including the crystal structures of [Pd(OAc)(ECH 2CH2CH2NMe2)]2· H2O (E = S, Se) and [PdCl(TeCH2CH2CH 2NMe2)]2
Dey, Sandip,Jain, Vimal K.,Varghese, Babu,Schurr, Thilo,Niemeyer, Mark,Kaim, Wolfgang,Butcher, Ray J.
, p. 1449 - 1457 (2008/10/09)
The reactions of the sodium salts of 3-dimethylamino-1- propylchalcogenolates, prepared by sodium borohydride reduction of (Me 2NCH2CH2CH2E)2 in methanol, with Na2PdCl4 yielded homoleptic [Pd(ECH 2CH2CH2NMe2)2] 6 (1) (E = S (1a); Se (1b); Te (1c)). When treated with [Pd(OAc) 2]3 or Na2PdCl4, compounds 1 readily gave binuclear redistribution products [PdX(ECH2CH 2CH2NMe2)]2 where X = OAc (2) (E = S (2a); Se (2b); or Cl (3)) (E = S (3a); Se (3b); Te (3c)), respectively. The terminal acetate/chloride ligands in 2b/3b can be substituted by other ionic ligands like PhSe-. The complexes were characterized by elemental analysis, UV-Vis, IR and NMR spectroscopy. The structures of 2a, 2b and 3c were established by X-ray crystallography. Each molecule has a dimeric structure in which there are two chalcogenolate bridges from the chelating 3-dimethylamino-1-propylchalcogenolate ligands. On pyrolysis, compound 2b affords Pd17Se15.
Synthesis and reactivity of a novel palladium germylene system
Cygan, Zuzanna T.,Bender IV, John E.,Litz, Kyle E.,Kampf, Jeff W.,Banaszak Holl, Mark M.
, p. 5373 - 5381 (2008/10/08)
The synthesis of three novel Pd germylene complexes is reported. (Ph3P)2PdGe[N(SiMe3)2]2 (1) was synthesized by ligand substitution of (Ph3P)4Pd, whereas (Et3P)PdGe[N(SiMe3)2]2 (2) and {appePdGe[N(SiMe3)2]2}2 (3b) (dppe = (diphenylphosphino)ethane) were synthesized by photolytic reduction of their corresponding phosphine oxalato complexes followed by addition of the germylene ligand. In solution, 3b exists in equilibrium with the monomeric dppePdGe[N(SiMe3)2]2 (3a). The germylene ligand of 2 was found to be 1 order of magnitude more labile than the analogous Pt system and 2 orders of magnitude less labile than the analogous Ni system. The reactivity of these new palladium germylenes toward O2 is described.
Structure and reactivity of (η3-indolylmethyl)palladium complexes generated by the reaction of organopalladium complexes with o-alkenylphenyl isocyanide
Onitsuka, Kiyotaka,Yamamoto, Mari,Suzuki, Shinobu,Takahashi, Shigetoshi
, p. 581 - 583 (2008/10/08)
Structure and reactivity of (η3-Indolylmethyl)palladium complexes generated by the reaction of organopalladium complexes with o-alkenylphenyl isocyanide were analyzed. The reaction of methylpalladium complexes with o-alkenylphenyl isocyanides r
Palladium-catalyzed insertion of 1,2- And 1,4-quinones into Si-Si bonds and its application to the modification of Si-Si-bond-containing polymers
Yamashita, Hiroshi,Reddy, N. Prabhakar,Tanaka, Masato
, p. 5223 - 5233 (2008/10/08)
Me3SiSiMe3 reacted with 1,2- and 1,4-quinones (p-benzoquinone (2a), its derivatives, 1,2-and 1,4-naphthoquinone, 9,10-phenanthraquinone (2f), 9,10-anthraquinone) in the presence of palladium catalysts to give the corresponding bis(trimethylsiloxy) aromatics in excellent to moderate yields. Active palladium catalysts were PdCl2L2 (L = tertiary phosphine) and Pd(dibenzylideneacetone)2-2P(OCH2)3CEt, among which PdCl2(PEt3)2 was in general the most efficient. A 1,2-disilacyclohexane cleanly underwent the reaction with 2f to form a 10-membered cyclic adduct. The reaction of Me3SiSiMe2SiMe3 with 2a also afforded p-(Me3SiO)2C6H4, via formal extrusion of a silylene unit. Treatment of cis-(PhMe2Si)2Pt(P-Me2Ph)2 with 2a gave p-(PhMe2SiO)2C6H4, indicative of the involvement of bis(silyl)palladium species in the catalysis. Quinones 2a,f smoothly underwent the palladium-catalyzed insertion into the Si-Si bonds of (SiMePhSiMePh-p-C6H4)n (9a), (SiMe2SiMe2CH2CH2)n, and (SiMe2SiMe2O)n to give partially or exhaustively modified polymers with arylenedioxy units incorporated in the backbones. A polysilane, (SiMe2)n, also reacted with 2a to provide a polymer with -SiMe2-O-p-C6H4-O- linkages. Upon UV irradiation, a partially modified polymer obtained from 9a and 2f showed a smaller extent of decrease in molecular weight than did the original polymer. Modification with 2f improved the thermal stability of 9a in thermogravimetric analysis.
Synthesis, reactions, and rearrangement of X(PR′3)2M[C(=PR)X] (M = Pt, Pd; X = Cl, Br; R′ = Et, Ph; R = 2,4,6-tri-tert-butylphenyl): Mechanism of the transition metal promoted conversion of X2C=PR to R-C≡P
Jun, Hyoung,Young Jr., Victor G.,Angelici, Robert J.
, p. 2444 - 2453 (2008/10/08)
Oxidative addition reactions of X2C=PR (X = Cl, Br; R = 2,4,6-tri-tert-butylphenyl) with M(PEt3)4 (M = Pt, Pd) or (C2H4)Pt(PPh3)2 initially yield the cis isomer of square planar (X)-(PR′3)2M[C(=PR)X] (II); these complexes (IIa-IId), where PR′3 is PEt3, rearrange rapidly in the presence of free PEt3 to give the trans isomers (Ia-Id). In contrast, the cis isomers (IIe and IIf), where PR′3 is PPh3 and M is Pt, react further to give R-C≡P and cis-X2Pt(PPh3)2. In polar solvents (CH2Cl2 and CHCl3), all the addition products (I and II) convert to R-C≡P and cis- or trans-X2M(PR′3)2 via the surprising phosphabicyclo intermediate (X)(PR′3)2Pt-(X-PBC) (III and IV); the structure of IIIa was established crystallographically. In the presence of H2O, (X)(PEt3)2Pt[C(=PR)X] (Ia and Ib where X = Cl, Br) give the oxophosphabicyclo complex (X)(PEt3)2Pt[(H)O=PBC] (Va and Vb) which was characterized by X-ray diffraction. A mechanism for the conversion of (X)(PR′3)2M[C(=PR)X] to R-C≡P and X2M-(PR′3)2 is proposed.
Synthesis and Characterization of Cyclometallated Complexes of Benzalazines. Crystal and Molecular Structure of 2>
Granell, Jaime,Sales, Joaquim,Vilarrasa, Jaume,Declercq, Jean P.,Germain, Gabriel,et al.
, p. 2441 - 2446 (2007/10/02)
The reaction of benzalazines, (p-RC6H4CH=N-)2 (R=H, Cl, NO2, or NMe2), with PdCl2 leads in the first two cases to the formation of cyclometallated polymeric species that react with phosphines to yield dimetallated compounds 2> (R'=Et or Ph) and/or .Phosphine exchange reactions give the complex 2>.The molecular structure of 2> has been determined by a single-crystal X-ray analysis.The crystals are monoclinic, space group P21/n, a=11.124(3), b=10.062(2), c=22.566(5) Angstroem, β=102.95(3) degree, and Z=2; R=0.052 for 3 306 reflections.Palladium atoms are five-co-ordinated, the Pd-N distance being 2.743 Angstroem.However, n.m.r. spectra show that, in solution, free rotation around the C(aromatic)-C(azomethine) bonds does occur even at -100 deg C.
Synthesis and characterization of tungsten oxo neopeniyiidene complexes1
Wengrovius, Jeffrey H.,Schrock, Richard R.
, p. 148 - 155 (2008/10/08)
Tantalum complexes of the type Ta(CHCMe3)X3(PR3)2 (X = Cl or Br) react with W(O)(OCMe3)4 to give [Ta(OCMe3)4X]2 and W(O)(CHCMe3)X2(PR
Photochemical Preparation of the cis Isomers of Dichlorobis(tri-n-alkyl-phosphine)palladium(II) (alkyl = Et, Prn, or Bun); the Crystal-structure Analysis of the Overcrowded n-Propyl Homologue
Alcock, Nathaniel W.,Kemp, Terence J.,Wimmer, Franz L.
, p. 635 - 638 (2007/10/02)
Ultraviolet irradiation of the trans forms of the title compounds in nitromethane gives up to 70percent of the labile cis isomers, which can be isolated in crystalline form.Irradiation of a 1:1 mixture of trans- and trans-n3)2Cl2> gives almost entirely a 1:1 mixture of the corresponding cis isomers and only a few percent of cis-n3)Cl2>, indicating a predominantly intramolecular mechanism.Crystals of cis-n3)2Cl2> are monoclinic, with space group P21/m, a=9.729(1), b=13.816(3), c=9.614(1) Angstroem, β=100.77(1) deg, and Z=2.The structure has been refined to R=0.029 for 1 873 reflections collected by a four-circle diffractometer.The cis-planar structure reveals considerable overcrowding .The Pd-P distances are short (mean 2.322 Angstroem) and the Pd-Cl distances long (mean 2.407 Angstroem), attributable to the trans effect.
