A simple and high-yield route to iridium, rhodium, osmium and ruthenium nido-6-metalladecaborane compounds

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F21%3A00548676" target="_blank" >RIV/61388963:_____/21:00548676 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/61388980:_____/21:00548676

Výsledek na webu

<a href="https://doi.org/10.1039/D1DT02971A" target="_blank" >https://doi.org/10.1039/D1DT02971A</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/d1dt02971a" target="_blank" >10.1039/d1dt02971a</a>

Jazyk výsledku

angličtina

Název v původním jazyce

A simple and high-yield route to iridium, rhodium, osmium and ruthenium nido-6-metalladecaborane compounds

Popis výsledku v původním jazyce

We report a high-yield heterogeneous solid/liquid phase synthetic method to a series of nido-6-metalladecaboranes. The hydridoirida- and hydridorhoda-decaboranes, [6,6,6-H(PPh3)(2)-nido-6-MB9H13] [M = Ir (1), Rh (2)] are isolatable in 98% yields from the reaction of the square-planar M(I) complexes, [MCl(PPh3)(3)] (M = Rh, Ir), with K[B9H14]. The same synthetic procedure, but using [MCl(CO)H(PPh3)(3)] (M = Ru, Os) as metal starting reagents produces the CO-ligated clusters, [6,6,6-(CO)(PPh3)(2)-nido-6-MB9H13] [M = Ru (3), Os (4)], in yields of 83% and 95%, respectively. These highly convenient syntheses permit the investigation of the reaction chemistry of the new nido-6-metalladecaboranes. Thus, the CO-ligated compounds, 3 and 4, react with the square-planar platinum(II) complex, [PtCl2(PMe2Ph)(2)], in the presence of potassium triethylborohydride, to give the bimetallic clusters, [1,1,1-(CO)H(PPh3)-isocloso-1-RuB9H8-mu-(1,2)-{Pt(PMe2Ph)(2)}] (5) and [7,7-(PMe2Ph)(2)-9,9,9-(CO)(PPh3)(2)-nido-7,9-PtOsB9H11] (6), and the monometallic nido-5-osamadecaborane, [5,5,5-(PPh3)(2)(CO)-nido-5-OsB9H13] (7). This reactivity illustrates the potential of polyhedral boron-based clusters as molecular scaffolds (“B-frames”) for the construction of multimetallic species. Single-crystal X-ray diffraction analyses have revealed the molecular structures of 3, 5, 6 and 7, the compounds are also studied by multielement NMR spectroscopy, mass spectrometry, IR spectroscopy, and in some cases computationally. Futhermore, the rotation of the {M(X)(PR3)(2)} moiety (X = H, CO), as PH3-ligated models, is studied by means of DFT-calculated relaxed potential energy surface scans, giving some insight into the lability of the metal-to-borane fragment interaction and of the exo-polyhedral ligands.

Název v anglickém jazyce

A simple and high-yield route to iridium, rhodium, osmium and ruthenium nido-6-metalladecaborane compounds

Popis výsledku anglicky

We report a high-yield heterogeneous solid/liquid phase synthetic method to a series of nido-6-metalladecaboranes. The hydridoirida- and hydridorhoda-decaboranes, [6,6,6-H(PPh3)(2)-nido-6-MB9H13] [M = Ir (1), Rh (2)] are isolatable in 98% yields from the reaction of the square-planar M(I) complexes, [MCl(PPh3)(3)] (M = Rh, Ir), with K[B9H14]. The same synthetic procedure, but using [MCl(CO)H(PPh3)(3)] (M = Ru, Os) as metal starting reagents produces the CO-ligated clusters, [6,6,6-(CO)(PPh3)(2)-nido-6-MB9H13] [M = Ru (3), Os (4)], in yields of 83% and 95%, respectively. These highly convenient syntheses permit the investigation of the reaction chemistry of the new nido-6-metalladecaboranes. Thus, the CO-ligated compounds, 3 and 4, react with the square-planar platinum(II) complex, [PtCl2(PMe2Ph)(2)], in the presence of potassium triethylborohydride, to give the bimetallic clusters, [1,1,1-(CO)H(PPh3)-isocloso-1-RuB9H8-mu-(1,2)-{Pt(PMe2Ph)(2)}] (5) and [7,7-(PMe2Ph)(2)-9,9,9-(CO)(PPh3)(2)-nido-7,9-PtOsB9H11] (6), and the monometallic nido-5-osamadecaborane, [5,5,5-(PPh3)(2)(CO)-nido-5-OsB9H13] (7). This reactivity illustrates the potential of polyhedral boron-based clusters as molecular scaffolds (“B-frames”) for the construction of multimetallic species. Single-crystal X-ray diffraction analyses have revealed the molecular structures of 3, 5, 6 and 7, the compounds are also studied by multielement NMR spectroscopy, mass spectrometry, IR spectroscopy, and in some cases computationally. Futhermore, the rotation of the {M(X)(PR3)(2)} moiety (X = H, CO), as PH3-ligated models, is studied by means of DFT-calculated relaxed potential energy surface scans, giving some insight into the lability of the metal-to-borane fragment interaction and of the exo-polyhedral ligands.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10406 - Analytical chemistry

Projekt

<a href="/cs/project/GA18-20286S" target="_blank" >GA18-20286S: Klastry hydridů boru pro lasery: Pochopení chemických a strukturálních faktorů, které určují fotofyziku anti-B18H22 a jejích derivátů</a><br>

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2021

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

1477-9234

Svazek periodika

50

Číslo periodika v rámci svazku

45

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

14

Strana od-do

16751-16764

Kód UT WoS článku

000717119100001

EID výsledku v databázi Scopus

2-s2.0-85120477514