Unexpected reaction of [Ni(CO)4-n(R2PCl)n] (n = 1, 2; R = But, Cy, Ph) with Na2[Fe2(CO)8]. Synthesis and electronic structure of the anions [Fe2(μ-CO)(CO)6(μ-Pr2)]− and their reactions with H+ and [M(PPh3)]+ (M = Cu, Ag, Au)

Copper‐Based Photosensitisers in Water Reduction: A More Efficient In Situ Formed System and Improved Mechanistic Understanding

“…Having established that [Cu(2a)(3a)] + is the speciesi nh ighest concentration, it wasi mportant to establish their relative reactivity,d ue to the possibility of as mall proportion of highly reactive PS responsible for the observeda ctivity.T od ot his, it was first necessary to confirmthat the observed Fe phosphidobridged dimer (5)i sa na ctive species.T hus 5 was indepen-dently synthesised, [39] and tested in combination with preformed [Cu(2a)(3a)] + and compared to the use of pre-catalyst trimer 4.W hen ensuringt he same number of Fe atoms are present,the same volume of H 2 was observed ( Figure 5), thereby confirming the role of 5 as an active WRC. This is consistent with previous studies that have shown improved activities with the addition of monodentate tris[3,5-bis(trifluoromethyl)phenyl] phosphine to [Fe 3 (CO) 12 ]( 4)i nc ombination with ap reformed stable Ir-based PS.…”

“…To do this, it was first necessary to confirm that the observed Fe phosphido‐bridged dimer ( 5 ) is an active species. Thus 5 was independently synthesised, and tested in combination with pre‐formed [Cu( 2 a )( 3 a )] + and compared to the use of pre‐catalyst trimer 4 . When ensuring the same number of Fe atoms are present, the same volume of H 2 was observed (Figure ), thereby confirming the role of 5 as an active WRC.…”

“…We would like to thank Andreas Koch for assistance with the quantitative ESI measurements, E. Oberema nd A. Rçsel forp reparation of compound 5 (see ref. [39]) and Dr.A .Spannenberg for X-ray crystallography.…”

Diferrate [Fe2(CO)6(μ‐CO){μ‐P(aryl)2}]− as Self‐Assembling Iron/Phosphor‐Based Catalyst for the Hydrogen Evolution Reaction in Photocatalytic Proton Reduction—Spectroscopic Insights

“…The immobilization could be realized in situ, for example, by application of diarylphosphine‐functionalized polystyrenes instead of molecular P(R) 3 . In addition, derivates that have not yet been accessible by the self‐assembly reaction could be applied as catalysts in molecular systems, for example, complexes of the type [Fe 2 (CO) 6 (μ‐CO){μ‐P(O^O)}] − or [Fe 2 (CO) 6 (μ‐CO){μ‐P(R) 2 }MY x ] . As regards the latter, with MY x =Cu(Bathocuproine), even light‐harvesting dyads are conceivable.…”

“…Synthesis of the complexes [NEt 4 ][2COP(c–f) 2 ] : [NEt 4 ][ 2 COP( e ) 2 ] was synthesized by the procedure reported by Walther et al . The other diferrates [NEt 4 ][ 2 COP( c ) 2 ], [NEt 4 ][ 2 COP( d ) 2 ], and [NEt 4 ][ 2 COP( f ) 2 ] were synthesized starting with the preparation of [NEt 4 ] 2 [Fe 2 (CO) 8 ] .…”