Synthesis and Reactivity of Nitridoruthenium(vi) Complexes of Weakly Coordinating Ligands

Abstract

Neutral, trialkylruthenium complexes Ru(N)R,L (R = CH,, CH,SiMe,; L = pyridine, 2,6-lutidine, 4-picoline, PMe,, CNCMe,) were prepared by the reaction of [Ru(N)R,]-salts with HBF4 and the ligand, L. The molecular ,structure of Ru(N)(CH,SiMe,,(py) was determined by X-ray diffraction. Crystals of Ru(N)(CH,SiMe, ,(py) are monoclinic in space group. P2,ln with a -14.551(5) A, b=9.113(4)& c = 19.801(5) a , a = y = 9 0 " , p = 109.27(2), 2 = 4 , R-0.032 and R,=0.039. The neutral dialkyl complex, Ru(N)R,CI, is in equilibrium with the dimer and adds a variety of neutral, two-electron ligands. Cationic complexes [Ru(N)R,L,][BF],] (R = CH,, CH,SiMe,;L = NCCH,, pyridine) were prepared by the reactions of Ru(N)R,L with HBF, and additional ligand. The addition of concentrated HN03(,,, to [Ru(NO)R,]-gave the nitrato complexes [Ru(N)R,(ONO,),]-. The complexes [Ru(N)R,L,][BF,] react with water to form the p-hydroxo dimers, {Ru(N)R,(p-OH)},. The molecular structure of {Ru(N)(CH),SiMe,),(pOH)} was determined by X-ray diffraction. Crystals of {Ru(N)(CH)]~S~M~,),(~-OH)} are monoclinic in space group P2,la with u -11.510(8) A, b=20.440(8) A, c=12.858(4) A, a = y = 9 0°, p=109.04, Z = 4 , R=0.027 and R,=0.029. The acetonitrile complex, [Ru(N)(CH,SiMe,),(NCMe),l[BF,], is a catalyst for the polymerization of ethylene.

Terminal Nitrido and Imido Complexes of the Late Transition Metals

“…These complexes are most numerous for Ru and Os; to date no Fe analogs have been synthesized. For ruthenium and osmium, type II species are known with many different types of equatorial ligands: halogens, [105][106][107][108][109][110][111][112] alkyl, [113][114][115][116][117][118][119][120][121][122] Nor O-donors, [55,[123][124][125][126][127][128][129] and thiolates [130][131][132][133][134][135] are known. Reactivity of these species is similar to those of type I, though it should be mentioned that the [OsNCl 4 ] -anion has been recently used as a cocatalyst (along with FeCl 3 ) for the oxidation of alkanes.…”

Recent developments in ruthenium nitrido complexes

“…69 Numerous Ru VI -nitrido complexes with mono-and/or bidentate ligand, such as relative alkyl, alkoxido, sulfido, diamino, dithio and amino acidic ligands, are generated via this way. [70][71][72][73][74][75][76][77] These nitrido compounds adopt geometry I or II. Their relatively stable Ru VI MN moieties are shown to be less reactive.…”

Dinuclear Ruthenium(III)–Ruthenium(IV) Complexes, Having a Doubly Oxido-Bridged and Acetato- or Nitrato-Capped Framework

“…Several dinuclear complexes having a doubly oxido-bridged core, M 2 (μ-O) 2 , e.g., Mn–Mn, Fe–Mn, Fe–Fe, and Co–Co, have been synthesized and characterized in relation to oxidation reactions catalyzed by metal complexes. Diruthenium complexes having a doubly oxido- or hydroxido-bridged core, Ru 2 (μ-O) 2 or Ru 2 (μ-OH) 2 , , and triply bridged diruthenium complexes, in which a bidentate ligand is capped between metal centers with the doubly oxido- or hydroxido-bridged core, have been reported. , In our previous work on dinuclear frameworks using a tridentate ancillary ligand, ethylbis­(2-pyridylmethyl)­amine (ebpma), triply chlorido- and/or methoxido-bridged diruthenium complexes of Ru II –Ru III , [{Ru­(ebpma)} 2 (μ-Cl) n (μ-OMe) 3– n ] 2+ ( n = 1, 3), , and singly oxido-bridged complexes of Ru III –Ru IV , [{RuX 2 (ebpma)} 2 (μ-O)] + (X = Cl, Br), have been synthesized. Their structures and reactivities, as well as their competency for functioning as molecular conversion reaction sites, have been of interest.…”