532-31-0Relevant articles and documents
Palladium nitrosyl carboxylate complexes X-ray structures of Pd 4(μ-NO)2(μ-OCOCMe3)6
Stromnova, Tatiana A.,Paschenko, Denis V.,Boganova, Lyubov' I.,Daineko, Mikhail V.,Katser, Sergei B.,Churakov, Andrei V.,Kuz'mina, Lyudmila G.,Howard, Judith A.K.
, p. 283 - 288 (2003)
Two types of palladium nitrosyl carboxylate complexes were synthesized and their structures were characterized by several methods including an X-ray diffraction analysis. The tetranuclear complexes Pd4(μ-NO) 2(OCOR)6 (R=CMe3, Me, Ph, CHMe2, CH2Cl, IIa-e, respectively) were synthesized by the reaction of Pd(NO)Cl with silver carboxylates Ag(OCOR). The structure of IIa was determined by a single crystal X-ray diffractometry. Crystals of IIa are monoclinic, space group P21/n, a=12.104(7), b=23.970(8), c=15.495(4) A?, β=90.30(4)°, V=4496(4) A?3. The least-square structure refinement on F2 was converged to R=0.0714 for 6228 reflections [I>2σ(I)]. In IIa the palladium atoms form near regular rectangle Pd4, with the edges bridged by the ligands. Two bridging NO groups occupying the opposite sides of the rectangle are in the cis-positions with respect to the Pd4 plane. These groups are symmetric, with the Pd-N-O angles ranging from 120.4(5) to 121.8(5)°. The coordination polyhedrons of the Pd atoms are close to square planar ones. The reaction of the Pd4(CO)4(OCOCF3)4 clusters with nitrogen monoxide leads to a substitution of the carbonyl groups and formation of the low stable complex Pd4(NO)4(OCOCF3) 4 (III) that was characterized by the spectroscopic and analytical data. The transformation of III during slow recrystallization from toluene gives Pd3(NO)2(OCOCF3) 4·2C6H5Me (IV) and palladium black. The structure of IV was determined by an X-ray diffraction analysis. Crystals of IV are monoclinic, space group P21/n, a=9.2340(2), b=9.2859(2), c=18.0460(4) A?, β=92.339(1)°, V=1546.08(6) A?3. The least-square refinement on F2 was converged to R=0.0205 for 3209 reflections [I>2σ(I)]. In the linear tri-nuclear molecule of IV, any adjacent metal atoms are linked with a couple of the CF3CO 2 ligands and are separated by 3.0755(2) A?. Additionally, the terminal Pd atoms bear the NO and the η2-toluene ligands. The configuration of the N atoms corresponds to the ideal sp2- hybridization. The Pd-N-O angle is 117.2(2)°. The N atoms form short contacts with the aromatic rings. The distance between the center of the ring and the nitrogen atom is 2.70 A?. Complex IV is the first example of the Pd complex with the terminal nitrosyl ligand. The scheme of transformation of complex III to complex IV was proposed.
Nucleophilic Opening of the Oxirane Ring with Tetraalkylammonium Salt Anions in the Presence of Proton Donors
Bakhtin, S. G.,Bespalko, Yu. N.,Shved, E. N.,Sinelnikova, M. A.
, p. 524 - 531 (2021/06/02)
Abstract: The behavior of tetraethylammonium salts in nucleophilic opening of the oxirane ring of epichlorohydrin (ECH) in the system ECH–proton donor–Et4N+ X–, where proton donor is benzoic acid or 4-nitrophenol and X = PhCOO or NO3, was studied by the kinetic and spectrophotometric methods. The order of the reaction in tetraethylammonium salt, benzoic acid, and 4-nitrophenol was estimated as first, zero, and less than zero, respectively. The mechanism of nucleophilic opening of the oxirane ring of ECH was elucidated on the basis of monitoring of the accumulation of 4-nitrophenoxide ion in the system ECH–4-nitrophenol–Et4NX upon variation of the initial concentrations of both tetraethylammonium salt and proton donor (4-nitrophenol) itself. The anion X of the initial tetraethylammonium salt was found to be irreversibly consumed as a result of its attack on the oxirane ring with participation of the proton donor, which led to generation of tetraethylammo-nium 4-nitrophenoxide, and the latter catalyzed the subsequent formation of the final product. An increase in the concentration of 4-nitrophenol was accompanied by reduction of both the rate of formation of 4-nitrophenoxide ion and the overall reaction rate, which corresponds to a mechanism involving nucleophilic attack of the anion X on the oxirane ring that is not activated by the proton donor.
SALT AND PHOTORESIST COMPOSITION CONTAINING THE SAME
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, (2011/02/18)
A salt represented by the formula (I—Pb): wherein Xpb represents a single bond or —O—, Rpb represents a single bond etc., Ypb represents a polymerizable group, Zpb represents an organic group, Xpc represents a single bond or a C1-C4 alkylene group, and Rpc represents a C1-C10 aliphatic hydrocarbon group which can have one or more substituents etc.
