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Title: Reactivity patterns of transition metal hydrides and alkyls

Abstract

The complex PPN/sup +/ CpV(CO)/sub 3/H/sup -/ (Cp=eta/sup 5/-C/sub 5/H/sub 5/ and PPN = (Ph/sub 3/P)/sub 2/) was prepared in 70% yield and its physical properties and chemical reactions investigated. PPN/sup +/ CpV(CO)/sub 3/H/sup -/ reacts with a wide range of organic halides. The organometallic products of these reactions are the vanadium halides PPN/sup +/(CpV(C)/sub 3/X)/sup -/ and in some cases the binuclear bridging hydride PPN/sup +/ (CpV(CO)/sub 3/)/sub 2/H/sup -/. The borohydride salt PPN/sup +/(CpV(CO)/sub 3/BH/sub 4/)/sup -/ has also been prepared. The reaction between CpV(CO)/sub 3/H/sup -/ and organic halides was investigated and compared with halide reductions carried out using tri-n-butyltin hydride. Results demonstrate that in almost all cases, the reduction reaction proceeds via free radical intermediates which are generated in a chain process, and are trapped by hydrogen transfer from CpV(CO)/sub 3/H/sup -/. Sodium amalgam reduction of CpRh(CO)/sub 2/ or a mixture of CpRh(CO)/sub 2/ and CpCo(CO)/sub 2/ affords two new anions, PPN/sup +/ (Cp/sub 2/Rh/sub 3/(CO)/sub 4/)/sup -/ and PPN/sup +/(Cp/sub 2/RhCo(CO)/sub 2/)/sup -/. CpMo(CO)/sub 3/H reacts with CpMo(CO)/sub 3/R (R=CH/sub 3/,C/sub 2/H/sub 5/, CH/sub 2/C/sub 6/H/sub 5/) at 25 to 50/sup 0/C to produce aldehyde RCHO and the dimers (CpMo(CO)/sub 3/)/sub 2/ and (CpMo(CO)/sub 2/)/submore » 2/. In general, CpV(CO)/sub 3/H/sup -/ appears to transfer a hydrogen atom to the metal radical anion formed in an electron transfer process, whereas CpMo(CO)/sub 3/H transfers hydride in a 2-electron process to a vacant coordination site. The chemical consequences are that CpV(CO)/sub 3/H/sup -/ generally reacts with metal alkyls to give alkanes via intermediate alkyl hydride species whereas CpMo(CO)/sub 3/H reacts with metal alkyls to produce aldehyde, via an intermediate acyl hydride species.« less

Authors:
Publication Date:
Research Org.:
California Inst. of Tech., Pasadena (USA)
OSTI Identifier:
5183113
Report Number(s):
LBL-10214
TRN: 80-014731
DOE Contract Number:  
W-7405-ENG-48
Resource Type:
Technical Report
Resource Relation:
Other Information: Thesis
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; COBALT COMPLEXES; CHEMICAL REACTIONS; CYCLOPENTADIENE; CHEMICAL PROPERTIES; MOLYBDENUM COMPLEXES; ORGANIC HALOGEN COMPOUNDS; REDUCTION; RHODIUM COMPLEXES; VANADIUM COMPLEXES; ALKYLATION; BOROHYDRIDES; CARBONYLS; CHEMICAL REACTION KINETICS; COMPLEXES; HYDRIDES; ORGANIC PHOSPHORUS COMPOUNDS; ORGANOMETALLIC COMPOUNDS; PHOSPHINES; ALKENES; BORON COMPOUNDS; CYCLOALKENES; DIENES; HYDROCARBONS; HYDROGEN COMPOUNDS; KINETICS; ORGANIC COMPOUNDS; PHOSPHORUS COMPOUNDS; POLYENES; REACTION KINETICS; TRANSITION ELEMENT COMPLEXES; 400301* - Organic Chemistry- Chemical & Physicochemical Properties- (-1987); 400201 - Chemical & Physicochemical Properties

Citation Formats

Jones, II, W D. Reactivity patterns of transition metal hydrides and alkyls. United States: N. p., 1979. Web. doi:10.2172/5183113.
Jones, II, W D. Reactivity patterns of transition metal hydrides and alkyls. United States. doi:10.2172/5183113.
Jones, II, W D. Tue . "Reactivity patterns of transition metal hydrides and alkyls". United States. doi:10.2172/5183113. https://www.osti.gov/servlets/purl/5183113.
@article{osti_5183113,
title = {Reactivity patterns of transition metal hydrides and alkyls},
author = {Jones, II, W D},
abstractNote = {The complex PPN/sup +/ CpV(CO)/sub 3/H/sup -/ (Cp=eta/sup 5/-C/sub 5/H/sub 5/ and PPN = (Ph/sub 3/P)/sub 2/) was prepared in 70% yield and its physical properties and chemical reactions investigated. PPN/sup +/ CpV(CO)/sub 3/H/sup -/ reacts with a wide range of organic halides. The organometallic products of these reactions are the vanadium halides PPN/sup +/(CpV(C)/sub 3/X)/sup -/ and in some cases the binuclear bridging hydride PPN/sup +/ (CpV(CO)/sub 3/)/sub 2/H/sup -/. The borohydride salt PPN/sup +/(CpV(CO)/sub 3/BH/sub 4/)/sup -/ has also been prepared. The reaction between CpV(CO)/sub 3/H/sup -/ and organic halides was investigated and compared with halide reductions carried out using tri-n-butyltin hydride. Results demonstrate that in almost all cases, the reduction reaction proceeds via free radical intermediates which are generated in a chain process, and are trapped by hydrogen transfer from CpV(CO)/sub 3/H/sup -/. Sodium amalgam reduction of CpRh(CO)/sub 2/ or a mixture of CpRh(CO)/sub 2/ and CpCo(CO)/sub 2/ affords two new anions, PPN/sup +/ (Cp/sub 2/Rh/sub 3/(CO)/sub 4/)/sup -/ and PPN/sup +/(Cp/sub 2/RhCo(CO)/sub 2/)/sup -/. CpMo(CO)/sub 3/H reacts with CpMo(CO)/sub 3/R (R=CH/sub 3/,C/sub 2/H/sub 5/, CH/sub 2/C/sub 6/H/sub 5/) at 25 to 50/sup 0/C to produce aldehyde RCHO and the dimers (CpMo(CO)/sub 3/)/sub 2/ and (CpMo(CO)/sub 2/)/sub 2/. In general, CpV(CO)/sub 3/H/sup -/ appears to transfer a hydrogen atom to the metal radical anion formed in an electron transfer process, whereas CpMo(CO)/sub 3/H transfers hydride in a 2-electron process to a vacant coordination site. The chemical consequences are that CpV(CO)/sub 3/H/sup -/ generally reacts with metal alkyls to give alkanes via intermediate alkyl hydride species whereas CpMo(CO)/sub 3/H reacts with metal alkyls to produce aldehyde, via an intermediate acyl hydride species.},
doi = {10.2172/5183113},
journal = {},
number = ,
volume = ,
place = {United States},
year = {1979},
month = {5}
}