Trans interaction in a metalcarbonyl. Structure of (Triphenylphosphinemethylide)diphenylphosphine oxide)=pentacarbonyltungsten(0), W(CO)5(O=P(C6H5)2CHP=(C6H5)3)

Reaction of Double Ylide C(PPh3)2 with [W(CO)6] – Crystal Structures of [(CO)5­W(CCPPh3)] and [(CO)5W{η1‐O2C2(PPh3)2}] and Bonding Analyses of [TM­(CCPR3)] Compounds

“…[25] When freshly prepared [(CO) 5 6 ] react in the same manner. [27] Earlier reports describe the formation of the adduct [Ph 3 PCHP{OW(CO) 5 }Ph 2 ], [28] which is not formed in our case. Such a complex would exhibit a pair of doublet signals in the 31 P NMR spectrum according to nonequivalent phosphorus atoms, and we believe that this adduct is not the result of the action of water on [(CO) 5 5 W-(C{PPh 3 } 2 )] was described and a signal at δ = 20.7 ppm in the 31 P NMR spectrum was assigned to this complex; [3] however, we believe that this signal is due to cation (Hǟ1) + , because this value is typical for (Hǟ1)X salts.…”

Formation and Crystal Structures of Lewis Acid Adducts of Ph3PCHP(O)Ph2; New Neutral and Cationic Species

“…With the C-P(O)Ph 2 bond length of 168.1(4) and the C-PPh 3 bond length of 171.6(4) a reverse situation to 2 occurs with a shifting of the partial double bond to the other side, more directed to the PO group. The same effects on the P-O bond are observed in 2 were a W(CO) 5 group is bonded to the oxygen atom instead of BF 3 , however, the related P-C bond lengths are those of 2, but according to large standard deviations in the tungsten complex, these values should be discussed with caution [6]. (5) with thermal ellipsoids at 40% probability, the hydrogen atoms are omitted for clarity.…”

“…Upon coordination of BF 3 at the O atom of 2, both doublets experienced a high field shift in the 31 [10] was isolated upon attempts to recrystallize the crude material from acetonitrile. The HI needed for protonation probably 6 formed upon borylation and deprotonation of the appropriate solvents. The 31 P NMR spectrum of 7 in DCM exhibits a doublet at 16.20 ppm ( 2 J(P,P) = 20.35 Hz) and a multiplet at 54.55 Hz, according to PPh 3 and P(OBI 3 )Ph 2 phosphorus atoms, respectively.…”

Divalent Carbon(0) Chemistry, Part 2: Protonation and Complexes with Main Group and Transition Metal Lewis Acids

“…It is noteworthy that the synthesis of 3-W(CO) 5 was reported more than 30 years ago by Kaska et al, [51] but attempts to obtain crystals which are suitable for X-ray diffraction analysis were unsuccessful. [51,52] The very high basicity of the divalent carbon(0) compounds will easily lead to side reactions, particularly in protic solvents, but the development of experimental methods in the last three decades may eventually lead to the isolation of complexes N-W(CO) 5 (N = 1-8). The synthesis of 5-W(CO) 5 and 5-Ni(CO) 3 would realize a new binding mode of carbon suboxide which has not been observed so far.…”