Pyrolysis of [Ru3(CO)10(dppe)]: activation of CH and PPh bonds.

Thermolysis of Ru3(CO)10(dppb): Activation of C H and P Ph bonds in PPh2P(CH2)4PPh2 (dppb = 1,4-bis(diphenylphosphino)butane)

“…The 1 H NMR spectrum of Bu n shows four multiplet peaks between d 2.71-2.40, 1.89-1.83, 1.41-1.34, 1.09-1.04 ppm for methylene chains and one triplet at d 0.62 ppm for the methyl group. Two broad peaks are observed between d 6.85-6.52 and 6.34 ppm for benzyne suggesting that there is movement of this fragment is around triruthenium triangle [6,12,21]. The multiplet peak between d 7.58 and 7.36 ppm is characterized as phenyl protons.…”

“…The structure of compound 1 and selected bond parameters are listed in the caption (Fig. 1), is derived from that of Ru 3 (CO) 12 by replacement of an equatorial carbonyl group on each of two Ru atoms by the P atoms of the bidentate phosphine ligand. The values of RuARu separations are in the range of 2.8448(1)-2.9053(2) Å with the longest RuARu bond is the one that is bridged by bidentate phosphine ligand which is similar to those found in Ru 3 (CO) 10 (dppe) [1] and Ru 3 (CO) 10 (dpph) [13].…”

“…Solvents were dried and distilled prior to use by standard methods. Ru 3 (CO) 12 and PPh 2 P(CH 2 ) 4 PPh 2 were purchased from Aldrich and used as received. Elemental analyses were performed using a Perkin Elmer Series II CHNS/O Analyzer 2400.…”

“…The cleavage of PAC or CAH bonds on the ligands are reported to cause the deactivation in homogeneous transition metal catalyst [9]. The thermolysis of Ru 3 (CO) 10 (dppm) in refluxing cyclohexane affords Ru 3 (CO) 9 [l 3 -PhPCH 2 PPh(C 6 H 4 )] as a result of one aryl CAP and one CAH cleavage [5,10] while the thermolysis of Os 3 (CO) 10 (dppm) in refluxing toluene yields unsaturated Os 3 (CO) 8 (CO) 10 (dppe) in refluxing toluene yields Ru 4 (CO) 9 (l-CO){l 4 -g 2 -PCH 2 CH 2 P(Ph) 2 }(l 4 -g 4 -C 6 H 4 )] [12]. Thus, the nuclearity of the cluster is preserved in products of Ru 3 (CO) 10 (dppm) while in Ru 3 (CO) 10 (dppe), there is a formation of tetranuclear complex.…”

The hydrogenation reaction of [Ru3(CO)10(C6F5)2P(CH2)2P(C6F5)2]: Migration of a C6F5 group from a phosphorus to a ruthenium atom. X-ray crystal structures of [Ru3(CO)9(μ-H){μ2-(C6F5)PCH2CH2P(C6F5)2}], [Ru3(CO)7(μ-H)3(η1-C6F5){μ3-PCH2CH2P(C6F5)2}] and [Ru3(CO)8(μ-H)2{μ3-PCH2CH2P(C6F5)2}]

“…The use of phosphine derived complexes revealed some differences with those of the unsubstituted carbonyl complexes [3], and these observations prompted other studies of the reactions of phosphine substituted clusters [4]. Some of these reactions showed that reaction pathways that transform the phosphine ligands are frequently observed [4,5] including activation of P-C bonds [6].…”