Cp(Prⁱ₂MeP)FeH₂SiR₃:  Nonclassical Iron Silyl Dihydride

Abstract

Reactions of a new borohydride complex 2 with hydrosilanes afford half-sandwich dihydride silyl complexes 3a-f. According to X-ray and DFT evidence complexes 3 have unprecedented double H...Si...H interligand interactions.

Nonclassical Ruthenium Silyl Dihydride Complexes TpRu(PPh3)(η3‐HSiR3H) [Tp = Hydridotris(pyrazolyl)borate]: Catalytic Hydrolytic Oxidation of Organosilanes to Silanols with TpRu(PPh3)(η3‐HSiR3H)

“…[2] Nikonov and co-workers have recently provided evidence from X-ray and DFT studies for the existence of H···Si···H bonding in the complex resulting from silane activation on the CpFe(iPr 2 MeP)H moiety; the complex is most appropriately formulated as CpFe-(iPr 2 MeP)(η 3 -H 2 SiR 3 ) (Figure 1). [3] Figure 1. Structure of CpFe(iPr 2 MeP)(η 3 -H 2 SiR 3 ).…”

N‐Heterocyclic Carbene Piano‐Stool Iron Complexes as Efficient Catalysts for Hydrosilylation of Carbonyl Derivatives

“…[17,18] Our interest in iron catalysis [19] and especially hydrosilylation [20,21] prompted us to examine the possibility of using NHC well-defined iron complexes in the hydrosilylation reaction. The report by Nikonov [22] using cationic [CpFe(phosphine)] complexes and the pioneer works from Brunner [23] oriented us towards piano-stool iron carbene complexes to catalyze such reduction reactions.To start our investigation, we have chosen to study well-defined iron complexes containing the IMes Nheterocyclic carbene ligand prepared by Guerchais: [13] the cationic complex 1 with one iodine as the counterion, and the neutral complex 2 obtained by photoirradiation of 1 in CH 2 Cl 2 (Figure 1). Herein, we report the efficient reduction of carbonyl compounds by hydrosilylation with these NHC-carbene piano-stool iron complexes.…”

Iron Dihydride Complex as the Pre‐catalyst for Efficient Hydrosilylation of Aldehydes and Ketones Under Visible Light Activation

“…[9] The other hydrosilylation approach was based on well-defined iron complexes as pre-catalysts: the pioneering Brunner CpFe(CO) 2 R system, [10] Gade bis(pyridylimino)isoindole pincer iron(II) catalyst, [11] or Nikonov CpFe(II)phosphinebased complex. [12] The use of such well-defined Fe(II) complexes as catalysts permits one to reach good activities (low catalyst loading and TON up 1000). Furthermore, iron(0) complexes were also useful in homogeneous catalysis.…”

“…[17e -i] As for aldehydes, the loading of the precatalyst can be decreased to 0.1 mol% when the reaction is performed at 100 8C for 2 h using 1 equivalent of diphenylsilane under light activation (Table 1, entries [12][13][14]. [20] Among the tested hydrosilanes, MeA C H T U N G T R E N N U N G (EtO) 2 SiH and (EtO) 3 SiH gave good GC yields in the corresponding alcohols.…”