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Dihydrogen complexes of osmium(II) t...

Li, Zai-Wei.

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Dihydrogen complexes of osmium(II) tetraamines: Preparation, characterization, reactivity and applications.

Record Type:	Language materials, printed : Monograph/item
Title/Author:	Dihydrogen complexes of osmium(II) tetraamines: Preparation, characterization, reactivity and applications./
Author:	Li, Zai-Wei.
Description:	194 p.
Notes:	Adviser: Henry Taube.
Contained By:	Dissertation Abstracts International54-05B.
Subject:	Chemistry, Biochemistry. -
Online resource:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=9326510

Dihydrogen complexes of osmium(II) tetraamines: Preparation, characterization, reactivity and applications.
Li, Zai-Wei.

Dihydrogen complexes of osmium(II) tetraamines: Preparation, characterization, reactivity and applications. - 194 p.

Adviser: Henry Taube.

Thesis (Ph.D.)--Stanford University, 1993.

A common isomerization from trans-$\rm\lbrack N\sb4Os\sp{II}(\eta\sp2$-H$\sb2)Subjects--Topical Terms:

1017722
Chemistry, Biochemistry.

Dihydrogen complexes of osmium(II) tetraamines: Preparation, characterization, reactivity and applications.
LDR:03266nam 2200337 a 45 001 937774
005 20110511
008 110511s1993 eng d
035 $a (UnM)AAI9326510
035 $a AAI9326510
040 $a UnM $c UnM
100 1 $a Li, Zai-Wei. $3 1261630
245 1 0 $a Dihydrogen complexes of osmium(II) tetraamines: Preparation, characterization, reactivity and applications.
300 $a 194 p.
500 $a Adviser: Henry Taube.
500 $a Source: Dissertation Abstracts International, Volume: 54-05, Section: B, page: 2498.
502 $a Thesis (Ph.D.)--Stanford University, 1993.
520 $a A common isomerization from trans-$\rm\lbrack N\sb4Os\sp{II}(\eta\sp2$-H$\sb2) $l ) to cis-$\rm\lbrack N\sb4Os\sp{II}(\eta\sp2$-H$\sb2) $l ) was found when L is a $\pi$-acid ligand or good $\sigma$-donor ligand.
520 $a By taking advantage of the facile substitution reaction, the complex $\rm\lbrack N\sb4Os(H\sb2)S\rbrack\sp{2+}$ has been used as a versatile recognition probe for biomolecules such as nucleotides, RNA, amino acids, peptides and phospholipids.
520 $a A new type of $\eta\sp2$-H$\sb2$ complex $\rm\lbrack N\sb4Os(H\sb2)S\rbrack\sp{2+}$ (where N$\sb4$ = (NH$\sb3)\sb4$ or (en)$\sb2,$ S is a solvent ligand) has been synthesized in aqueous solution by reduction of $\rm(NH\sb3)\sb4Os\sp{III}(CF\sb3SO\sb3)\sb3$ or $\rm\lbrack en\sb2Os\sp{VI}O\sb2\rbrack(CF\sb3SO\sb3)\sb2$ by Zn/Hg. A facile substitution reaction has been discovered involving replacement of a labile oxygen donor solvent ligand $\rm S(H\sb2O,\ CH\sb3OH,\ (CH\sb3)\sb2CO)$ by a wide range of ligands, L, leading to a new series of $\eta\sp2$-H$\sb2$ complexes $\rm\lbrack N\sb4Os\sp{II}(H\sb2)L\rbrack.$
520 $a Each new species was characterized by $\sp1 $h NMR, IR, UV spectroscopy, X-ray or neutron diffractions and the affinity of the Os(II) center for the ligand L was studied. Judged by UV-vis spectroscopic evidence and pK$\sb{\rm b}$ measurement, $\eta\sp2$-H$\sb2$ is a somewhat stronger $\pi$ acid ligand than pyridine.
520 $a The $\eta\sp2$-H$\sb2$ complexes $\rm\lbrack N\sb4Os\sp{II}(H\sb2)L\rbrack$ undergo a 2e$\sp-$ oxidation, which is unusual for Os(II) complexes, giving seven coordinate, 18 e$\sp-,$ paramagnetic Os(IV) monohydride species, which in the presence of $\pi$-acid ligands can been converted to six coordinate diamagnetic Os(II) complexes by deprotonation. The process is reversible.
520 $a The unusual properties which include the wide range of J(HD) values as L is changed, the high affinity of $\rm \lbrack N\sb4 Os\sp{II}(H\sb2)\rbrack\sp{2+}$ for most ligands L, both saturated and unsaturated, the sensitivity of the rates of isomerization and oxidation to the variable ligand L, the labilizing effect of H$\sb2$ on the rates of substitution of L can be explained by the adjustment of Os-H$\sb2$ bonding, from Os(II)-$\eta\sp2$-dihydrogen to Os(IV)-dihydride, in the complexes, a kind of adjustment unique to H$\sb2.$
590 $a School code: 0212.
650 4 $a Chemistry, Biochemistry. $3 1017722
650 4 $a Chemistry, Inorganic. $3 517253
650 4 $a Chemistry, Physical. $3 560527
690 $a 0487
690 $a 0488
690 $a 0494
710 2 0 $a Stanford University. $3 754827
773 0 $t Dissertation Abstracts International $g 54-05B.
790 $a 0212
790 1 0 $a Taube, Henry, $e advisor
791 $a Ph.D.
792 $a 1993
856 4 0 $u http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=9326510