Controlled Reactivity of Terminal Cyaphide Complexes: Isolation of the 5-Coordinate [Ru(dppe)₂(C≡P)]⁺

Abstract

R (2019) Controlled reactivity of terminal cyaphide complexes: Isolation of the 5-coordinate [Ru(dppe)2(CP)]+. Inorganic Chemistry.

A Cyaphide Transfer Reagent

“…Unlike cyanide, which forms a multitude of stable salts, the cyaphide ion, CP – , cannot be obtained as a simple A­(CP) or Ae­(CP) 2 salt (where A = alkali and Ae = alkaline-earth metal). To date, the CP – ion has only ever been isolated in the coordination sphere of three metals (platinum, ruthenium, and uranium; e.g., trans -[Ru­(dppe) 2 (H)­(CP)] where dppe = bis­(1,2-diphenyl­phosphinoethane) − and an electrophilic borane . While these studies demonstrate that the ion is accessible, the resulting compounds are of limited synthetic utility due to their inertness.…”

Pnictogen‐Functionalised C1 Ligands: MC‐ARn (n=0, 1, 2, 3)

“…The vacant coordinations ite in [83] + allows coordination of additional ligands, for example, treatment with Me 2 Mg or LiCCPh regenerates 81 and 79 d,r espectively,w hereas CO coordinates to gives [Ru(h 1 -C P)(CO)(dppe) 2 ] + [84] + .L igand addition should allow aw ide range of new cyaphide complexes to be prepared, and as such this is an especially promising precursor for the further developmento fc yaphide chemistry. [76] Attempts by Russella nd co-workerst og enerate molybdenum cyaphide complexes using nucleophilic desilylation procedures analogous to those employed for ruthenium have so far been largely unsuccessful, although the formation of [Mo(C P)(P CSiMe 3 )(dppe) 2 ] À has been inferredo nt he basis of 31 PNMR data. [77] Grützmacher,M eyer and co-workers recently reported an ew strategyf or the synthesis of au ranium(IV) cyaphide complex by an unusual CÀOb ond cleavage of phosphaethynolate, À OCP,b ye xploitingt he oxophilicity and redox properties of tri-valentu ranium.T reatment of [U{N(OAr Ad,Me ) 3 }(DME)] (N(OAr Ad,Me ) 3 3À = tris(2-hydroxy-3-(1-adamantyl)-5-methylbenzyl)amine trianion;D ME = dimethoxyethane) with [Na(OCP)-(dioxane) 2.5 ]f ollowed by 2.2.2-cryptand gives the binuclear, moxo-bridged U IV derivative [U 2 (h 1 -C P){N(OAr Ad,Me ) 3 } 2 (m-O)(DME)] À ([85] À ;S cheme 23).…”

“…The vacant coordination site in [ 83 ] + allows coordination of additional ligands, for example, treatment with Me 2 Mg or LiC≡CPh regenerates 81 and 79 d , respectively, whereas CO coordinates to gives [Ru(η 1 ‐C≡P)(CO)(dppe) 2 ] + [ 84 ] + . Ligand addition should allow a wide range of new cyaphide complexes to be prepared, and as such this is an especially promising precursor for the further development of cyaphide chemistry [76] …”

Revealing the Role of the Cyaphide Ion as a Bridging Ligand in Heterometallic Complexes

“…[M]À C�P). [8][9][10][11][12][13] The dearth of known cyaphido complexes is largely due to the fact that, until recently, there was not a widely applicable route available for their synthesis. Heavier analogues of nitriles, so-called phosphaalkynes (RÀ C�P), have been studied much more widely.…”

“…Selected bond lengths [Å] and angles [°]: Au1À C1 1.991(4), Au1À C2 2.025(4), C1À P1 1.605(4), C1À Rh1 2.159(4), P1À Rh1 2.297(2), P1À W1 2.499(1), Rh1À P2 2.233(2), Rh1À Cp*(cent.) 1.903; C1-Au1-C2 174.7(2), Au1-C1-P1 155.4(3), C1-P1-W1 144.57(16), C1-Rh1-P1 42.09(11).…”