Transition Metal Complexes Containing Monotertiary Arsines and Stibines

CloydJr, J. C.; McAuliffe, Charles A.

doi:10.1007/978-1-349-81558-6_3

Cited by 6 publications

(2 citation statements)

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“…(1) Dative-bond formation or complexation of Me3As by electrophiles, such as transition metal cations, M (15) may occur. In some instances, such transition metal binding sites may themselves be of enzymatic importance to another biological process, thereby producing altered, possibly toxic, secondary effects in another organism (16).…”

Section: Introductionmentioning

confidence: 99%

Questions concerning Environmental Mobility of Arsenic: Needs for a Chemical Data Base and Means for Speciation of Trace Organoarsenicals

Brinckman¹,

Parris²,

Blair³

et al. 1977

Environmental Health Perspectives

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Biomethylation of metals, including arsenic, apparently occurs as a global process. Health control strategies therefore depend on accurate analysis of arsenic's environmental mobility. Determining to what extent biotransformations occur and how resultant organometal(loids) are sequestered in food chains requires sophistication beyond present-day total element determinations. Rather, active molecular forms of arsenic must be speciated for each environmental compartment, and it is necessary to quantify the dynamics of arsenic's mobility. Thus, new chemical facts are needed yielding rates of methylation or demethylation of arsenic; partition coefficients of organoarsenicals between air, water, and organic phases; and arsenic redox chemistry in polar media. NBS research in this context is reviewed with examples of recent results emphasizing speciation methodology. Topic areas discussed are: the nature of aquated methylarsenic species (NMR and laser-Raman spectroscopy); transport of methylarsenicals from aqueous media (gas chromatography-graphite furnace AA detection applied to metabolic Me3As formation); and speciation of involatile organoarsenicals in aqueous media (demonstration of HPLC utilizing element-specific AA detection and appraisal of electrochemical detectors). Introduction Biotransformations of metalloids such as arsenic have been known for years, but only in recent times has the ubiquitous biomethylation of arsenic (1) and a number of other elements, including heavy metals (2-4), become apparent as a general environmental process (5). Clearly, anthropogenic inputs in inorganic materials can and do enhance such transformations , resulting in transport of volatile or lipid-soluble pollutants. Moreover, there is evidence (6) that even higher organisms, specifically man, can invoke elimination processes which involve formation of methylarsenic compounds. Consequently,

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Section: Introductionmentioning

confidence: 99%

Questions concerning Environmental Mobility of Arsenic: Needs for a Chemical Data Base and Means for Speciation of Trace Organoarsenicals

Brinckman¹,

Parris²,

Blair³

et al. 1977

Environmental Health Perspectives

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“…Simultaneously, we decided to investigate the preparation of MOFs based on triarylarsines (AsAr 3 ), referred to as arsine coordination materials (ACMs). To the best of our knowledge, there are no prior reports of triarylarsine-based MOFs, even though arsines are commonplace in organometallic chemistry . Organoarsines are structurally and chemically similar to organophosphines but are less basic because the As-4 sp 3 lone pair is more diffuse.…”

mentioning

confidence: 99%

Organoarsine Metal–Organic Framework with cis-Diarsine Pockets for the Installation of Uniquely Confined Metal Complexes

et al. 2018

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ACM-1 is the first example of an organoarsine metal-organic framework (MOF), prepared using a new pyridyl-functionalized triarylarsine ligand coordinated to Ni(II) nodes. ACM-1 has micropores that are decorated with cis-diarsine coordination pockets. Postsynthetic metalation of ACM-1 with AuCl under facile conditions studied by single-crystal X-ray diffraction reveals the installation of dimeric AuCl complexes via the formation of As-Au bonds. The Au(I) dimers display exceptionally short aurophilic bonds (2.76 Å) induced by the rigidity of the MOF, which acts as a unique solid-state ligand.

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