Preparation, Properties, and Reactions of Metal‐Containing Heterocycles, XCV. Transition‐Metal‐Mediated Cyclocotrimerization of Selenophosphinites with Activated Alkynes

Abstract

Selenophosphinito complexes (OC)4Mn(η2‐Se\documentclass{article}\usepackage{amsmath}\pagestyle{empty}\begin{document}$ \dddot - $\end{document}PR21) (2a, b) [R1 = cyc‐Hex (a), tBu (b)] are formed by the reaction of BrMn(CO)5 with the phosphane selenides R21HPSe (1a, b) in the presence of the auxiliary base Et(iPr)2N. According to an X‐ray structural analysis, 2a crystallizes in the space group \documentclass{article}\pagestyle{empty}\begin{document}$ P\bar 1 $\end{document} with Z = 2. The dimeric complex [(OC)4Mn(μ‐Se\documentclass{article}\usepackage{amsmath}\pagestyle{empty}\begin{document}$ \dddot - $\end{document}PMe2)]2 (4c) is not obtained in a straightforward way. Compound 4c is only obtained via the intermediate Br(OC)4Mn–Se\documentclass{article}\usepackage{amsmath}\pagestyle{empty}\begin{document}$ \dddot - $\end{document}P(H)Me2 (3c) by HBr elimination with nBuLi. Complex 3c is formed by replacement of carbon monoxide in BrMn(CO)5 by Me2HPSe (1c). A dissociative equilibrium between [(OC)4 Mn(μ‐Se\documentclass{article}\usepackage{amsmath}\pagestyle{empty}\begin{document}$ \dddot - $\end{document}PMe2)]2 (4c) and the monomeric species (OC)4Mn(\documentclass{article}\usepackage{amsmath}\pagestyle{empty}\begin{document}$ \dddot - $\end{document}2‐Se\documentclass{article}\usepackage{amsmath}\pagestyle{empty}\begin{document}$ \dddot - $\end{document}PMe2) was not observed. The cyclocotrimerization of the >P\documentclass{article}\usepackage{amsmath}\pagestyle{empty}\begin{document}$ \dddot - $\end{document}Se function with the activated alkynes ZCCZ [Z = CO2R2; R2 = Me (d), Et (e), iPr (f), cyc‐Hex (g)] was successful only in the case of the cyclohexyl derivative 2a to give the selenaphosphamanganabicycloheptadienes 5d – g. An X‐ray structural analysis proved that 5d crystallizes in the space group \documentclass{article}\pagestyle{empty}\begin{document}$ P\bar 1 $\end{document} with Z = 2. Under CO pressure 5d was degraded to the selenophene 6.

Pentamethylcyclopentadienyl Ruthenium Complexes with Sulfur- and Selenium-Donor Ligands

“…The diselenophosphinate [Se 2 P( i -Pr) 2 ] - binds to Ru in an approximate symmetric η 2 mode [Ru−Se distances being 2.543(2) and 2.538(2) Å], while the selenophosphinite [SeP( i -Pr) 2 ] - ligand is in an unusual η 2 -(Se,P) mode with the P(2)−Ru(1)−Se(3) bite angle of 51.98°. Metal complexes with η 2 -selenophosphinite ligands are rather rare . The P−Se(3) bond distance of 2.166(4) Å for 7 is short and comparable to that in [Mn(CO) 5 (η 2 -SePCy 2 )],19c indicative of PSe double bond character.…”

Reactions of ether-phosphine ruthenium hydride complexes with carbon disulfide and phenylacetylene: crystal structures of Ru(CO) Cl(P ∼ O)3(η2-S2CH and Ru(CO) Cl(P ∼ O)2(η2-S2CH)

“…Compared with the bis(chelate)ruthenium complexes ClzRu(P n 0) 2 [18], the starting compounds RuC1H(P n O)(P ~ O) z (la,b) show a different behavior toward phenylacetylene. Instead of the formation of r/Lvinylidene complexes, hydrogen is evolved and the acetylide complexes RuCI(P n O)2(C=CPh) (5a,b) are formed.…”

Discrete copper(i) clusters with Cu6P6Se6 and Cu6P4Se6 cores

“…Previously reported coordination modes for selenophosphinites are shown in Scheme 1 (modes I, II and III). 5,10,11 Therefore in 1 two new bonding geometries for selenophosphinites are observed-coordination modes IV and V. Four of the selenophosphinite ligands in 1 adopt coordination mode IV, bridging three copper centres: m 1 from P and m 2 from Se (P-Se = 2.233(2), 2.255(2) A ˚). The remaining two selenophosphinites are present in coordination mode V, bridging four metal centres: m 1 from P and m 3 from Se (P-Se = 2.336(2) A ˚).…”

“…These Ph 2 PSeCH 2 Se 2 ligands coordinate m 1 to Cu(3) from the phosphorus centre and m 3 to Cu(1A), Cu(3) and Cu(6) from the selenolate atom Se(5), hence forming a five membered chelate with Cu(3). The P-Se and C-Se bonds within this chelate are all single bonds: P(4)-Se(10) = 2.236(3), Se(10)-C(1) = 1.991 (10), C(1)-Se(5) = 1.937(10) A ˚. Formation of the chelate ring also results in the extrusion of the phosphorus P(4) from the central core of the cluster to yield a new Cu 6 P 4 Se 6 core.…”