Ruthenium Benzylidene and Vinylidene Complexes in a Sulfur-Rich Coordination Environment

Abstract

Interaction of Ru(CHPh)(PCy3)2Cl2 (Cy = cyclohexyl) with K[N(PPh2S)2] affords air-stable Ru(CHPh)[N(PPh2S)2]2, 1, which has been characterized by X-ray diffraction. The Ru−Cα and average Ru−S distance for 1 are 1.88(2) and 2.377 Å, respectively. Reaction of 1 with CO gives cis-Ru(CO)2[N(PPh2S)2]2. Complex 1 undergoes metathesis with ethyl vinyl ether to give the methoxycarbene complex Ru(CHOEt)[N(PPh2S)2]2, 3. Treatment of Ru(CHPh)(PCy3)2Cl2 with K[N(PPh2Se)2] affords Ru(CHPh)[PPh2NP(Se)Ph2]2, 4, which has been characterized by X-ray crystallography. The Ru−C, average Ru−P, and average Ru−Se distances are 1.873(8), 2.383, and 2.450 Å, respectively. Reactions of Ru(CHPh)(PCy3)2Cl2 with K[P(OR)2S2] afford cis-Ru(CHPh)(PCy3)[P(OR)2S2]2 (R = Et (6) and i-Pr (7)). Reaction of Ru(CHPh)(PCy3)2Cl2 with 1,4,7-trithiacyclononane ([9]aneS3) gives [([9]aneS3)Ru(CHPh)(PCy3)Cl]Cl, 8. Treatment of Ru(CCHPh)(PCy3)2Cl2 with K[N(PPh2S)2] or [9]aneS3 affords cis-Ru(CCHPh)(PCy3)[N(PPh2S)2]2 (9) or ([9]aneS3)Ru(PCy3)Cl2 (10), respectively. The Ru−C, Ru−P, and average Ru−S distances in 9 are 1.80(1), 2.420(3), and 2.479 Å, respectively. Complexes 1 and 8 are active catalysts for ring-opening metathesis polymerization of norbornene.

Morphology control of the magnetization reversal mechanism in Co80Ni20 nanomagnets

“…∼ 0.6 times the one of the cylinder having d = 10 nm) as reported in previous works(author?) [3,22,23,24,25,26,27]. These results are, to our knowledge, the first experimental proof of the existence of a morphology factor that corrects the magnetization reversal mechanism mainly driven by the shape aspect ratio.…”

“…[5,13,24]. This method has shown an accurate size control of the nanoparticles via the kinetic control of the growth step (author?)…”

“…This method has shown an accurate size control of the nanoparticles via the kinetic control of the growth step (author?) [6,24]. Briefly, in this soft chemistry route, the liquid polyol acts as a solvent and as a reducing agent for the metallic cation.…”

“…It is now also well established that length and diameter size can play an important role over the static magnetic properties of different shaped nanowires (e.g. coercivities meltdown can be easily observed with increasing diameter and decreasing length of the nanowires) [3,[22][23][24][25][26][27]. Studies of the head-morphology effect on the reversal mechanism are less evident and, to our knowledge, still an experimental open issue.…”

Manganese and rhenium triphosphorus macrocycle complexes and reactions with alkenes

“…The compound 9[ane]S 3 Ru(᎐ ᎐ CHPh)(PCy 3 )Cl] ϩ does ring-open norbornene giving rise to good yields of polymer after 2 h at room temperature (92%, M n = 2.7 × 10 5 , PDi = 3.5) and the authors suggest that ligand dissociation occurs before alkene coordination. 25 The performance of these complexes (quoted as yields by the authors) indicate that our Re and Ru compounds compare very favourably with literature values, indeed 1 Et appears to be significantly more effective as it polymerises norbornene in excellent yield (Table 1) but in shorter timescales (1 h) and under milder conditions (0 ЊC).…”