Silver(I) complexes with 1 '-(diphenylphosphino)-1-cyanoferrocene: the art of improvisation in coordination

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11310%2F16%3A10325132" target="_blank" >RIV/00216208:11310/16:10325132 - isvavai.cz</a>

Výsledek na webu

<a href="http://dx.doi.org/10.1039/c6dt01843b" target="_blank" >http://dx.doi.org/10.1039/c6dt01843b</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/c6dt01843b" target="_blank" >10.1039/c6dt01843b</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Silver(I) complexes with 1 '-(diphenylphosphino)-1-cyanoferrocene: the art of improvisation in coordination

Popis výsledku v původním jazyce

1'-(Diphenylphosphino)-1-cyanoferrocene (1) reacts with silver(I) halides at a 1:1 metal-to-ligand ratio to afford the heterocubane complexes [Ag(mu(3)-X)(1-kappaP)]4, where X = Cl (2), Br (4), and I (5). In addition, the reaction with AgCl with 2 equiv. of 1 leads to chloride-bridged dimer [(mu-Cl)2{Ag(1-kappaP)2}2] (3) and, presumably, also to [(mu(P,N)-1){AgCl(1-kappaP)}]2 (3'). While similar reactions with AgCN furnished only the insoluble coordination polymer [(1-kappaP)2Ag(NC)Ag(CN)]n (6), those with AgSCN afforded the heterocubane [Ag(1-kappaP)(mu-SCN-S,S,N)]4 (7) and the thiocyanato-bridged disilver(I) complex [Ag(1-kappaP)2(mu-SCN-S,N)]2 (8), thereby resembling reactions in the AgCl-1 system. Attempted reactions with AgF led to ill-defined products, among which [Ag(1-kappaP)(2)(mu-HF2)]2 (9) and [(mu-SiF6){Ag(1-kappaP)2}2] (10) could be identified. The latter compound was prepared also from Ag2[SiF6] and 1. Reactions between 1 and AgClO4 or Ag[BF4] afforded disilver complexes [(mu(P,N)-1)Ag(ClO4-kappaO)]2 (11) and [(mu(P,N)-1)Ag(BF4-kappaF)]2 (12) featuring pseudolinear Ag(I) centers that are weakly coordinated by the counter anions. A similar reaction with Ag[SbF6] followed by crystallization from ethyl acetate produced an analogous complex, albeit with coordinated solvent, [(mu(P,N)-1)Ag(AcOEt-kappaO)]2[SbF6]2 (13). Ultimately, a compound devoid of any additional ligands at the Ag(I) centers, [(mu(P,N)-1)Ag]2[B(C6H3(CF3)2-3,5)4]2 (14), was obtained from the reaction of 1 with silver(I) tetrakis[3,5-bis(trifluoromethyl) phenyl] borate. The reaction of Ag[BF4] with two equivalents of 1 produced unique coordination polymer [Ag(1-kappaP)(mu(P,N)-1)]n[BF4] n (15), the structure of which contained one of the phos-phinoferrocene ligands coordinated as a P, N-chelate and the other forming a bridge to an adjacent Ag(I) center.

Název v anglickém jazyce

Silver(I) complexes with 1 '-(diphenylphosphino)-1-cyanoferrocene: the art of improvisation in coordination

Popis výsledku anglicky

1'-(Diphenylphosphino)-1-cyanoferrocene (1) reacts with silver(I) halides at a 1:1 metal-to-ligand ratio to afford the heterocubane complexes [Ag(mu(3)-X)(1-kappaP)]4, where X = Cl (2), Br (4), and I (5). In addition, the reaction with AgCl with 2 equiv. of 1 leads to chloride-bridged dimer [(mu-Cl)2{Ag(1-kappaP)2}2] (3) and, presumably, also to [(mu(P,N)-1){AgCl(1-kappaP)}]2 (3'). While similar reactions with AgCN furnished only the insoluble coordination polymer [(1-kappaP)2Ag(NC)Ag(CN)]n (6), those with AgSCN afforded the heterocubane [Ag(1-kappaP)(mu-SCN-S,S,N)]4 (7) and the thiocyanato-bridged disilver(I) complex [Ag(1-kappaP)2(mu-SCN-S,N)]2 (8), thereby resembling reactions in the AgCl-1 system. Attempted reactions with AgF led to ill-defined products, among which [Ag(1-kappaP)(2)(mu-HF2)]2 (9) and [(mu-SiF6){Ag(1-kappaP)2}2] (10) could be identified. The latter compound was prepared also from Ag2[SiF6] and 1. Reactions between 1 and AgClO4 or Ag[BF4] afforded disilver complexes [(mu(P,N)-1)Ag(ClO4-kappaO)]2 (11) and [(mu(P,N)-1)Ag(BF4-kappaF)]2 (12) featuring pseudolinear Ag(I) centers that are weakly coordinated by the counter anions. A similar reaction with Ag[SbF6] followed by crystallization from ethyl acetate produced an analogous complex, albeit with coordinated solvent, [(mu(P,N)-1)Ag(AcOEt-kappaO)]2[SbF6]2 (13). Ultimately, a compound devoid of any additional ligands at the Ag(I) centers, [(mu(P,N)-1)Ag]2[B(C6H3(CF3)2-3,5)4]2 (14), was obtained from the reaction of 1 with silver(I) tetrakis[3,5-bis(trifluoromethyl) phenyl] borate. The reaction of Ag[BF4] with two equivalents of 1 produced unique coordination polymer [Ag(1-kappaP)(mu(P,N)-1)]n[BF4] n (15), the structure of which contained one of the phos-phinoferrocene ligands coordinated as a P, N-chelate and the other forming a bridge to an adjacent Ag(I) center.

Druh

J_x - Nezařazeno - Článek v odborném periodiku (Jimp, Jsc a Jost)

CEP obor

CA - Anorganická chemie

OECD FORD obor

—

Projekt

<a href="/cs/project/GA13-08890S" target="_blank" >GA13-08890S: Polární ferrocenové amidofosfinové ligandy pro katalytické aplikace</a><br>

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2016

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Dalton Transactions

ISSN

1477-9226

e-ISSN

—

Svazek periodika

45

Číslo periodika v rámci svazku

26

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

17

Strana od-do

10655-10671

Kód UT WoS článku

000379352900020

EID výsledku v databázi Scopus

2-s2.0-84976553254