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81.
82.
During the course of studies directed towards the synthesis of kinetically stable silver(I) complexes, we have prepared a hexadentate bis-[9]-NS2 ligand (1) which may be expected to form a series of stable octahedral complexes with many transition metal ions. The silver(I) complex has been characterized spectroscopically and crystallographically. 相似文献
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85.
Joyce McMahon Frankie P. Anderson John F. Gallagher Alan J. Lough 《Acta Crystallographica. Section C, Structural Chemistry》2008,64(9):o493-o497
The isomers 2,3‐, (I), 2,4‐, (II), and 2,5‐difluoro‐N‐(4‐pyridyl)benzamide, (III), all with formula C12H8F2N2O, all exhibit intramolecular C—H...O=C and N—H...F contacts [both with S(6) motifs]. In (I), intermolecular N—H...O=C interactions form one‐dimensional chains along [010] [N...O = 3.0181 (16) Å], with weaker C—H...N interactions linking the chains into sheets parallel to the [001] plane, further linked into pairs via C—H...F contacts about inversion centres; a three‐dimensional herring‐bone network forms via C—H...π(py) (py is pyridyl) interactions. In (II), weak aromatic C—H...N(py) interactions form one‐dimensional zigzag chains along [001]; no other interactions with H...N/O/F < 2.50 Å are present, apart from long N/C—H...O=C and C—H...F contacts. In (III), N—H...N(py) interactions form one‐dimensional zigzag chains [as C(6) chains] along [010] augmented by a myriad of weak C—H...π(arene) and O=C...O=C interactions and C—H...O/N/F contacts. Compound (III) is isomorphous with the parent N‐(4‐pyridyl)benzamide [Noveron, Lah, Del Sesto, Arif, Miller & Stang (2002). J. Am. Chem. Soc. 124 , 6613–6625] and the three 2/3/4‐fluoro‐N‐(4‐pyridyl)benzamides [Donnelly, Gallagher & Lough (2008). Acta Cryst. C 64 , o335–o340]. The study expands our series of fluoro(pyridyl)benzamides and augments our understanding of the competition between strong hydrogen‐bond formation and weaker influences on crystal packing. 相似文献
86.
Lee K Clark TJ Lough AJ Manners I 《Dalton transactions (Cambridge, England : 2003)》2008,(20):2732-2740
The Fe and Ru phosphine-borane complexes CpM(CO)2PPh2 x BH3 (1, M = Fe, 4, M = Ru) were synthesized utilizing the reaction of the phosphine-borane anion Li[PPh2 x BH3] with the iodo complexes CpM(CO)2I. The Fe complex 1 reacted with PMe3 to yield CpFe(CO)(PMe3)(PPh2 x BH3) (2) and CpFe(PMe3)2(PPh2 x BH3) (3) whereas the Ru species 4 gave only CpRu(CO)(PMe3)(PPh2 x BH3) (5). The complexes 1-5 were characterized by 1H, 11B, 13C and 31P NMR spectroscopy, MS, IR and X-ray crystallography for 1 to 4, and EA for 1, 2 and 4. The reactivity of 1 and 4 towards PPh2H x BH3 was explored. Although no stoichiometric reactions were detected under mild conditions, both 1 and 4 were found to function as dehydrocoupling catalysts to afford Ph2PH x BH2 x PPh2 x BH3 in the melt at elevated temperature (120 degrees C). The carbonyl Fe2(CO)9 also functioned as a dehydrocoupling catalyst under similar conditions. Complex 1 and Fe2(CO)9 represent the first reported active Fe complexes for the catalytic dehydrocoupling of phosphine-borane adducts. 相似文献
87.
Huynh K Rivard E Lough AJ Manners I 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(12):3431-3440
A series of DMAP-stabilized (DMAP=4-dimethylaminopyridine) N-silylphosphoranimine cations [DMAPPR(2)==NSiMe(3)](+), bearing R=Cl ([8](+)), Me ([10 a](+)), Me/Ph ([10 b](+)), Ph ([10 c](+)), and OCH(2)CF(3) ([10 d](+)) substituents, have been synthesized from the reactions of the parent phosphoranimines Cl(3)P==NSiMe(3) (3) and XR(2)P==NSiMe(3) (X=Cl (9), Br (11); R=Me (9 a and 11 a), Me/Ph (9 b and 11 b), Ph (9 c and 11 c), and OCH(2)CF(3) (9 d and 11 d)) with DMAP and silver salts as halide abstractors. Reactions in the absence of silver salts yield the corresponding cations, with halide counterions. The stability of the salts is highly dependent on the phosphoranimine substituent and the nature of the counteranion, such that electron-withdrawing substituents and non-coordinating anions yield the most stable salts. X-ray structural determination of the cations reveal extremely short phosphoranimine P--N bond lengths for the cations [8](+) and [10 d](+) (1.47-1.49 A) in which electron-withdrawing substituents are present and a longer phosphoranimine P--N length for the cation [10 a](+) (1.53 A) in which electron-donating substituents are present. Very wide bond angles at nitrogen are observed for the salts containing the cation [10 d](+) (158-166 degrees ) and indicate significant sp hybridization at the nitrogen centre. 相似文献
88.
The photopolymerisation of sila[1]ferrocenophane [Fe(eta-C5H4)2SiMe2] (3) with 4,4',4'-tri-tert-butyl-2,2':6',2'-terpyridine (tBu3terpy) as initiator has been explored. High-molecular-weight polyferrocenylsilane (PFS) [{Fe(eta-C5H4)2SiMe2}n] (5) was formed in high yield when a stoichiometric amount of tBu3terpy was used at 5 degrees C. Photopolymerisation of ferrocenophane 3 at higher temperatures gave PFS 5 in lower yield and with a reduced molecular weight as a result of a slower propagation rate. Remarkably, when Me3SiCl was added as a capping agent before photopolymerisation, subsequent photolysis of the reaction mixture resulted in the unprecedented cleavage of both iron-Cp bonds in ferrocenophane 3: iron(II) complex [Fe(tBu3terpy)2Cl2] (7Cl) was formed and the silane fragment (C5H4SiMe3)2SiMe2 (8) was released. The iron-Cp bond cleavage reaction also proceeded in ambient light, although longer reaction times were required. In addition, the unexpected cleavage chemistry in the presence of Me3SiCl was found to be applicable to other photoactive ferrocenes such as benzoylferrocene. For benzoylferrocene and ferrocenophane 3, the presence of metal-to-ligand charge transfer (MLCT) character in their low-energy transitions in the visible region probably facilitates photolytic iron-Cp bond cleavage, but this reactivity is suppressed when the strength of the iron-Cp bond is increased by the presence of electron-donating substituents on the cyclopentadienyl rings. 相似文献
89.
Equilibrium constants (K) for reactions between acids and the conjugate base forms of a number of phosphonium salts, [HPR3][BF4], and iron hydrides, [Fe(CO)3H(PR3)2][BF4], in CD(2)Cl(2) have been determined by means of 31P and 1H NMR spectroscopy at 20 degrees C. The anchor compound chosen for pK(CD(2)Cl(2)) determinations was [HPCy3][BF4] with a pK(CD(2)Cl(2)) value of 9.7, as assigned by literature convention (Cy: cyclohexyl). A continuous scale of pK(CD(2)Cl(2)) values covering the range from 9.7 to -3 was created and correlated with the DeltaH values reported by Angelici and co-workers and literature pK(a) values. The pK(CD(2)Cl(2)) values for 15 other hydride or dihydrogen complexes of the iron group elements and of diethyl ether were also placed on this scale. The crystal structures of [Fe(CO)3H(PCy(2)Ph)2][BF4] and [Fe(CO)3(PCy(2)Ph)2] revealed that the trans-oriented, bulky, unsymmetrical phosphane ligands distort the equatorial plane of the complexes. The acidity of iron carbonyl hydrides is an important feature of the reactions of iron hydrogenase enzymes. 相似文献
90.
Bertoli M Choualeb A Gusev DG Lough AJ Major Q Moore B 《Dalton transactions (Cambridge, England : 2003)》2011,40(35):8941-8949
This paper reports the synthesis, structure, and properties of a series of PNP pincer complexes of osmium OsH(3)Cl[HN(C(2)H(4)P(i)Pr(2))(2)] (1), OsH(3)[N(C(2)H(4)P(i)Pr(2))(2)] (2), OsH(4)[HN(C(2)H(4)P(i)Pr(2))(2)] (3), and OsH(2)(PMe(3))[HN(C(2)H(4)P(i)Pr(2))(2)] (4). The tetrahydride 3 operates as an efficient catalyst at 0.1 mol% loading for the reactions of amination and dehydrogenative coupling of primary alcohols, producing secondary amines and symmetrical esters, respectively. The catalyst 3 is distinguished by outstanding stability, and it can be used in an aqueous environment at temperatures as high as 200 °C. 相似文献