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1.
Padavattan Govindaswamy Patrick J. Carroll Yurij A. Mozharivskyj Mohan Rao Kollipara 《Journal of Chemical Sciences》2006,118(4):319-326
The reaction of [{(η5-C5Me5)M(μ-Cl)Cl}2] {where M = Rh (1), Ir (2)} with functionalized phosphine viz., diphenyl-2-pyridylphosphine (PPh2Py) in dichloromethane solvent yield neutral ϰ1-P-coordinated rhodium and iridium complexes [(η5-C5Me5)RhCl2(κ1-P-PPh2Py)]3 and [(η5-C5Me5) IrCl2(ϰ1-P-PPh2Py)]4. Reaction of complexes 1 and 2 with the ligand PPh2Py in methanol under reflux give bis-substituted complexes such as [(η5-C5Me5)RhCl(ϰ1-P-PPh2Py)2]+
5 and [(η5-C5Me5)IrCl(ϰ1-P-PPh2Py)2]+
6, whereas stirring in methanol at room temperature gives P-, N-chelating complexes of the type [(η5-C5Me5)RhCl(ϰ2-P-N-PPh2Py)]+ 7 and [(η5-C5Me5)IrCl(ϰ2-P-N-PPh2Py)]+
8. Neutral ϰ1-P-coordinated complexes [(η5-C5Me5)RhCl2(ϰ1-P-PPh2Py)]3 and [(η5-C5Me5)IrCl2(ϰ1-P-PPh2Py)]4 easily undergo conversion to the cationic P-, N-chelating complexes [(η5-C5Me5)RhCl(ϰ2-P-N-PPh2Py)]+
7 and [(η5-C5Me5) IrCl(ϰ2-P, N-PPh2Py)]+
8 on stirring in methanol at room temperature. These complexes are characterized by FT-IR and FT-NMR spectroscopy as well as
analytical methods. The molecular structures of the representative complexes [(η5-C5Me5)RhCl2(ϰ1-P-PPh2Py)]3, [(η5-C5Me5)IrCl2(ϰ1-P-PPh2Py)]4 and hexafluorophosphate salt of complex [(η5-C5Me5)IrCl(ϰ2-P-PPh2Py)2]+
6 are established by single-crystal X-ray diffraction methods 相似文献
2.
Electric fields of the anions, cations and neutral forms of 2-aminopurine and 6-thioguanine have been mapped. Certain important
features of the maps are similar to those found earlier in the neutral and ionic forms of adenine and guanine. The computed
electric field patterns satisfactorily explain reactive sites and biological activity of the molecules. 相似文献
3.
This article studies some geometrical aspects of the semidefinite linear complementarity problem (SDLCP), which can be viewed as a generalization of the well-known linear complementarity problem (LCP). SDLCP is a special case of a complementarity problem over a closed convex cone, where the cone considered is the closed convex cone of positive semidefinite matrices. It arises naturally in the unified formulation of a pair of primal-dual semidefinite programming problems. In this article, we introduce the notion of complementary cones in the semidefinite setting using the faces of the cone of positive semidefinite matrices and show that unlike complementary cones induced by an LCP, semidefinite complementary cones need not be closed. However, under R0-property of the linear transformation, closedness of all the semidefinite complementary cones induced by L is ensured. We also introduce the notion of a principal subtransformation with respect to a face of the cone of positive semidefinite matrices and show that for a self-adjoint linear transformation, strict copositivity is equivalent to strict semimonotonicity of each principal subtransformation. Besides the above, various other solution properties of SDLCP will be interpreted and studied geometrically. 相似文献
4.
5.
A simple and versatile method for the synthesis of acetals from aldehydes and ketones using bismuth triflate 总被引:1,自引:0,他引:1
Leonard NM Oswald MC Freiberg DA Nattier BA Smith RC Mohan RS 《The Journal of organic chemistry》2002,67(15):5202-5207
Acetals are obtained in good yields by treatment of aldehydes and ketones with trialkyl orthoformate and the corresponding alcohol in the presence of 0.1 mol % Bi(OTf)3.4H2O. A simple procedure for the formation of acetals of diaryl ketones has also been developed. The conversion of carbonyl compounds to the corresponding 1,3-dioxolane using ethylene glycol is also catalyzed by Bi(OTf)3.4H2O (1 mol %). Two methods, both of which avoid the use of benzene, have been developed. 相似文献
6.
Mohan MM 《Physical review. B, Condensed matter》1993,48(17):12478-12482
7.
The microwave-assisted dry media technology was utilized for the synthesis of some novel derivatives in the Hantzsch—Biginelli reaction. In this eco-friendly approach, the usage of organic solvents and hazardous reagents resulting in corrossion of materials was minimized, giving high yields of products within a short reaction time. 相似文献
8.
T. L. Luke H. Mohan V. M. Manoj P. Manoj J. P. Mittal C. T. Aravindakumar 《Research on Chemical Intermediates》2003,29(4):379-391
Reactions of sulphate radical anion (SO·4
-) with 4,6-dihydroxy-2-methyl pyrimidine (DHMP), 2,4-dimethyl-6-hydroxy pyrimidine (DMHP), 6-methyl uracil (MU) and 5,6-dimethyl uracil (DMU) have been studied by pulse radiolysis at pH 3 and at pH 10. The transient intermediate spectra were compared with those from the reaction of hydroxyl radical (·OH). It is proposed that SO·4
- produces radical cations of these pyrimidines in the initial stage. These radical cations are short-lived except in the case of DMHP where a relatively longer lived radical cation is proposed to be formed. When there is a hydrogen atom attached to the N(1) or N(3) position, a deprotonation from these sites is highly favored. When there is no hydrogen attached to these sites, deprotonation from a substituted methyl group is favored. At acidic pH, deprotonation from nitrogen is observed for DHMP, MU and DMU. At basic pH, the radical cation reacts with OH- leading to the formation of OH adducts. 相似文献
9.
R. Krishna Mohan Rao Kallury Pramod V. Upadhyaya Tumbalam G. Surendra Nath Vankipuram R. Srinivasan 《Journal of mass spectrometry : JMS》1977,12(5):307-312
The mass spectra of eight 1,2,4-triazole derivaties have been recorded and found tao reveal extensive hydrogen and skeletal migrations. The structures of the fragments have been confirmed by deuterium labelling and exact mass measurement. The compounds revealed striking differences in their spectra depending on the nature of the substituents. 相似文献
10.
Ulrich Vgeli Wolfgang von Philipsborn Kuppuswamy Nagarajan Mohan D. Nair 《Helvetica chimica acta》1978,61(2):607-617
Heterocyclic compounds obtained by addition of acetylenedicarboxylic acid esters to thioureas, cyclic amidines and o-difunctionalized aromatic systems have been studied by 13C-NMR. In particular, C, H-spin-coupling constants over two and three bonds were used to differentiate between the various constitutional isomers and to establish the configuration of trisubstituted exocyclic C, C-double bonds. The configurational significance and diagnostic value of vicinal cis and trans C,H-spin coupling is again demonstrated in the present series. 相似文献