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      A Cyaphide Transfer Reagent

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          Abstract

          The cyanide ion plays a key role in a number of industrially relevant chemical processes, such as the extraction of gold and silver from low grade ores. Metal cyanide compounds were arguably some of the earliest coordination complexes studied and can be traced back to the serendipitous discovery of Prussian blue by Diesbach in 1706. By contrast, heavier cyanide analogues, such as the cyaphide ion, C≡P , are virtually unexplored despite the enormous potential of such ions as ligands in coordination compounds and extended solids. This is ultimately due to the lack of a suitable synthesis of cyaphide salts. Herein we report the synthesis and isolation of several magnesium–cyaphido complexes by reduction of i Pr 3SiOCP with a magnesium(I) reagent. By analogy with Grignard reagents, these compounds can be used for the incorporation of the cyaphide ion into the coordination sphere of metals using a simple salt-metathesis protocol.

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          Most cited references43

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          Theoretical Chemistry of Gold

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            Triple-Bond Covalent Radii

            A system of additive covalent radii is proposed for sigma(2) pi(4) triple bonds involving elements from Be to E 112 (eka-mercury). Borderline cases with weak multiple bonding are included. Only the elements in Group 1, the elements Zn-Hg in Group 12 and Ne in Group 18 are then totally excluded. Gaps are left at late actinides and some lanthanides. The standard deviation for the 324 included data points is 3.2 pm.
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              A N-heterocyclic carbene gold hydroxide complex: a golden synthon

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                Author and article information

                Journal
                J Am Chem Soc
                J Am Chem Soc
                ja
                jacsat
                Journal of the American Chemical Society
                American Chemical Society
                0002-7863
                1520-5126
                30 June 2021
                14 July 2021
                : 143
                : 27
                : 10367-10373
                Affiliations
                [1]Department of Chemistry, Chemistry Research Laboratory, University of Oxford , 12 Mansfield Road, Oxford OX1 3TA, U.K.
                Author notes
                Author information
                https://orcid.org/0000-0002-9092-0200
                https://orcid.org/0000-0002-7311-1663
                Article
                10.1021/jacs.1c04417
                8297854
                34190545
                0bf8fde4-af70-4aca-b193-55eec6fb8c61
                © 2021 The Authors. Published by American Chemical Society

                Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained ( https://creativecommons.org/licenses/by/4.0/).

                History
                : 28 April 2021
                Funding
                Funded by: Engineering and Physical Sciences Research Council, doi 10.13039/501100000266;
                Award ID: EP/S023828/1
                Funded by: University of Oxford, doi 10.13039/501100000769;
                Award ID: NA
                Funded by: Engineering and Physical Sciences Research Council, doi 10.13039/501100000266;
                Award ID: EP/T010681/1
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                ja1c04417
                ja1c04417

                Chemistry
                Chemistry

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