The dominant steric effect in the synthesis of ammine hydrido- and chlorido-Ru(II)-N,N-dimethylhydrazine and mixed alkyl-aryl phosphine complexes: Novel methyldiazene reduction intermediates

Frederick P. Malan; Afsar Ali; Eric Singleton; Reinout Meijboom

doi:10.1016/j.ica.2015.08.019

The dominant steric effect in the synthesis of ammine hydrido- and chlorido-Ru(II)-N,N-dimethylhydrazine and mixed alkyl-aryl phosphine complexes: Novel methyldiazene reduction intermediates

Frederick P. Malan, Afsar Ali, Eric Singleton, Reinout Meijboom

Chemical Sciences

University of Johannesburg

Research output: Contribution to journal › Article › peer-review

3 Citations (Scopus)

Abstract

Novel cationic hydrido complexes [RuH(1,5-cod)(NH₃)(NH₂NMe₂)₂](X) (X = PF₆, BPh₄) and chlorido-ammine complexes [RuCl(1,5-cod)(NH₃)₂(NH₂NMe₂)](X) (X = PF₆, BPh₄), were isolated from the reaction of the polymeric [RuCl₂(1,5-cod)]_x with NH₂NMe₂. Reaction of the hydrido complexes with the phosphine ligands PMe₃, PMe₂Ph, P(OMe)₂Ph resulted in the formation of monohydrido-phosphine complexes, whereas reaction with the bulkier PMePh₂ ligand gave dihydrido-phosphine complexes. Similar reactions of the chlorido-ammine complexes with the phosphine ligands PMe₃, PMe₂Ph, P(OMe)₂Ph, and PMePh₂ all sequentially substituted the NH₂NMe₂ and the 1,5-cod ligands to give the chlorido-ammine phosphine complexes. All complexes were fully characterised and the single crystal X-ray structures were determined for [RuH{P(OMe)₂Ph}₅](BPh₄), [RuH₂(PMePh₂)₄], [{Ru(PMe₂Ph)₃}₂(μ-F)₃](PF₆), fac-[RuCl(NH₃)₂(PMe₂Ph)₃](PF₆), and [RuCl(NH₃)(PMe₂Ph)₄](PF₆). Intramolecular strain between coordinated σ-donor ligands in the Ru(II)-NH₂NMe₂ precursor complexes as well as the relative steric bulk of incoming σ-donor ligands were found to be chemically directing in the formation of monohydrido-, bishydrido-, mono-ammine, and bis-ammine ruthenium(II) complexes.

Original language	English
Pages (from-to)	133-142
Number of pages	10
Journal	Inorganica Chimica Acta
Volume	437
DOIs	https://doi.org/10.1016/j.ica.2015.08.019
Publication status	Published - 1 Oct 2015

Keywords

Cationic
Dimethylhydrazine
Intramolecular strain
Nitrogenase
Ruthenium

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry

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10.1016/j.ica.2015.08.019

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@article{d8c789f0848248f783dc3408757a5568,

title = "The dominant steric effect in the synthesis of ammine hydrido- and chlorido-Ru(II)-N,N-dimethylhydrazine and mixed alkyl-aryl phosphine complexes: Novel methyldiazene reduction intermediates",

abstract = "Novel cationic hydrido complexes [RuH(1,5-cod)(NH3)(NH2NMe2)2](X) (X = PF6, BPh4) and chlorido-ammine complexes [RuCl(1,5-cod)(NH3)2(NH2NMe2)](X) (X = PF6, BPh4), were isolated from the reaction of the polymeric [RuCl2(1,5-cod)]x with NH2NMe2. Reaction of the hydrido complexes with the phosphine ligands PMe3, PMe2Ph, P(OMe)2Ph resulted in the formation of monohydrido-phosphine complexes, whereas reaction with the bulkier PMePh2 ligand gave dihydrido-phosphine complexes. Similar reactions of the chlorido-ammine complexes with the phosphine ligands PMe3, PMe2Ph, P(OMe)2Ph, and PMePh2 all sequentially substituted the NH2NMe2 and the 1,5-cod ligands to give the chlorido-ammine phosphine complexes. All complexes were fully characterised and the single crystal X-ray structures were determined for [RuH{P(OMe)2Ph}5](BPh4), [RuH2(PMePh2)4], [{Ru(PMe2Ph)3}2(μ-F)3](PF6), fac-[RuCl(NH3)2(PMe2Ph)3](PF6), and [RuCl(NH3)(PMe2Ph)4](PF6). Intramolecular strain between coordinated σ-donor ligands in the Ru(II)-NH2NMe2 precursor complexes as well as the relative steric bulk of incoming σ-donor ligands were found to be chemically directing in the formation of monohydrido-, bishydrido-, mono-ammine, and bis-ammine ruthenium(II) complexes.",

keywords = "Cationic, Dimethylhydrazine, Intramolecular strain, Nitrogenase, Ruthenium",

author = "Malan, {Frederick P.} and Afsar Ali and Eric Singleton and Reinout Meijboom",

year = "2015",

month = oct,

day = "1",

doi = "10.1016/j.ica.2015.08.019",

language = "English",

volume = "437",

pages = "133--142",

journal = "Inorganica Chimica Acta",

issn = "0020-1693",

publisher = "Elsevier BV",

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The dominant steric effect in the synthesis of ammine hydrido- and chlorido-Ru(II)-N,N-dimethylhydrazine and mixed alkyl-aryl phosphine complexes: Novel methyldiazene reduction intermediates. / Malan, Frederick P.; Ali, Afsar; Singleton, Eric et al.
In: Inorganica Chimica Acta, Vol. 437, 01.10.2015, p. 133-142.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - The dominant steric effect in the synthesis of ammine hydrido- and chlorido-Ru(II)-N,N-dimethylhydrazine and mixed alkyl-aryl phosphine complexes

T2 - Novel methyldiazene reduction intermediates

AU - Malan, Frederick P.

AU - Ali, Afsar

AU - Singleton, Eric

AU - Meijboom, Reinout

PY - 2015/10/1

Y1 - 2015/10/1

N2 - Novel cationic hydrido complexes [RuH(1,5-cod)(NH3)(NH2NMe2)2](X) (X = PF6, BPh4) and chlorido-ammine complexes [RuCl(1,5-cod)(NH3)2(NH2NMe2)](X) (X = PF6, BPh4), were isolated from the reaction of the polymeric [RuCl2(1,5-cod)]x with NH2NMe2. Reaction of the hydrido complexes with the phosphine ligands PMe3, PMe2Ph, P(OMe)2Ph resulted in the formation of monohydrido-phosphine complexes, whereas reaction with the bulkier PMePh2 ligand gave dihydrido-phosphine complexes. Similar reactions of the chlorido-ammine complexes with the phosphine ligands PMe3, PMe2Ph, P(OMe)2Ph, and PMePh2 all sequentially substituted the NH2NMe2 and the 1,5-cod ligands to give the chlorido-ammine phosphine complexes. All complexes were fully characterised and the single crystal X-ray structures were determined for [RuH{P(OMe)2Ph}5](BPh4), [RuH2(PMePh2)4], [{Ru(PMe2Ph)3}2(μ-F)3](PF6), fac-[RuCl(NH3)2(PMe2Ph)3](PF6), and [RuCl(NH3)(PMe2Ph)4](PF6). Intramolecular strain between coordinated σ-donor ligands in the Ru(II)-NH2NMe2 precursor complexes as well as the relative steric bulk of incoming σ-donor ligands were found to be chemically directing in the formation of monohydrido-, bishydrido-, mono-ammine, and bis-ammine ruthenium(II) complexes.

AB - Novel cationic hydrido complexes [RuH(1,5-cod)(NH3)(NH2NMe2)2](X) (X = PF6, BPh4) and chlorido-ammine complexes [RuCl(1,5-cod)(NH3)2(NH2NMe2)](X) (X = PF6, BPh4), were isolated from the reaction of the polymeric [RuCl2(1,5-cod)]x with NH2NMe2. Reaction of the hydrido complexes with the phosphine ligands PMe3, PMe2Ph, P(OMe)2Ph resulted in the formation of monohydrido-phosphine complexes, whereas reaction with the bulkier PMePh2 ligand gave dihydrido-phosphine complexes. Similar reactions of the chlorido-ammine complexes with the phosphine ligands PMe3, PMe2Ph, P(OMe)2Ph, and PMePh2 all sequentially substituted the NH2NMe2 and the 1,5-cod ligands to give the chlorido-ammine phosphine complexes. All complexes were fully characterised and the single crystal X-ray structures were determined for [RuH{P(OMe)2Ph}5](BPh4), [RuH2(PMePh2)4], [{Ru(PMe2Ph)3}2(μ-F)3](PF6), fac-[RuCl(NH3)2(PMe2Ph)3](PF6), and [RuCl(NH3)(PMe2Ph)4](PF6). Intramolecular strain between coordinated σ-donor ligands in the Ru(II)-NH2NMe2 precursor complexes as well as the relative steric bulk of incoming σ-donor ligands were found to be chemically directing in the formation of monohydrido-, bishydrido-, mono-ammine, and bis-ammine ruthenium(II) complexes.

KW - Cationic

KW - Dimethylhydrazine

KW - Intramolecular strain

KW - Nitrogenase

KW - Ruthenium

UR - http://www.scopus.com/inward/record.url?scp=84941551992&partnerID=8YFLogxK

U2 - 10.1016/j.ica.2015.08.019

DO - 10.1016/j.ica.2015.08.019

M3 - Article

AN - SCOPUS:84941551992

SN - 0020-1693

VL - 437

SP - 133

EP - 142

JO - Inorganica Chimica Acta

JF - Inorganica Chimica Acta

ER -

The dominant steric effect in the synthesis of ammine hydrido- and chlorido-Ru(II)-N,N-dimethylhydrazine and mixed alkyl-aryl phosphine complexes: Novel methyldiazene reduction intermediates

Abstract

Keywords

ASJC Scopus subject areas

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