Site of Bond Breaking in mer-(Dihapto-[60]fullerene) (Dihapto-1, 2-Bis-(Diphenylphosphino)ethane Tricarbonyl Tungsten(0)

A biphasic displacement of [60]fullerene from fac-(dihapto-[60]fullerene)(dihapto-1,10-phenanthroline) tricarbonyl molybdenum (0)

“…Dichloromethane was nitrogen-purged to yield %0.017 g (ca. 25% yield) of a yellowish-brown solid identified as fac-(g 2 -C 60 )(g 2 -phen)Mo(CO) 3 …”

“…In fact, due to this high electron affinity, its chemical and physical properties are similar to those of electron-deficient olefins [13,14]. The assertion that [60]fullerene can act as a r-Lewis base is supported by the observation that it can compete with Lewis bases such as triphenylphosphine, tricyclohexylphosphine, and triethyl phosphite for coordination sites in electronically deficient transition metal carbonyl complexes [1][2][3]. The claim that observation that piperidine (pip) displaces dppe from mer-(g 2 -C 60 )(g 2 -dppe)W(CO) 3 to produce mer-(g 2 -C 60 ) (g 1 -pip) 2 W(CO) 3 exclusively [3].…”

“…Studies of the ligand exchange reactions on the complexes (g 2 -C 60 )W(CO) 5 [1], fac-(g 2 -C 60 )(g 2 -phen)W-(CO) 3 [2], and mer-(g 2 -C 60 )(g 2 -dppe)W(CO) 3 [3], (dppe = 1,2-bis(diphenylphosphino)ethane, phen = 1, 10-phenanthroline) have shown that (i) [60]fullerene is a good p-acceptor and a good r-Lewis base, (ii) the W-C 60 bond enthalpy is in the vicinity of 105-109 kJ/ mol [1,2] and (iii) [60]fullerene can be a labilizing ligand [4,5]. The p-acceptor capacity of [60]fullerene can be explained on the basis that [60]fullerene has a strong tendency to accept electrons [6][7][8][9][10][11][12].…”

“…The assertion that [60]fullerene can act as a r-Lewis base is supported by the observation that it can compete with Lewis bases such as triphenylphosphine, tricyclohexylphosphine, and triethyl phosphite for coordination sites in electronically deficient transition metal carbonyl complexes [1][2][3]. The claim that observation that piperidine (pip) displaces dppe from mer-(g 2 -C 60 )(g 2 -dppe)W(CO) 3 to produce mer-(g 2 -C 60 ) (g 1 -pip) 2 W(CO) 3 exclusively [3]. On the other hand, the observation that PPh 3 displaces C 60 from fac-(g 2 -C 60 )(g 2 -phen)W(CO) 3 is consistent with the strong cis-labilizing nature of phenanthroline [5,15].…”

“…The claim that observation that piperidine (pip) displaces dppe from mer-(g 2 -C 60 )(g 2 -dppe)W(CO) 3 to produce mer-(g 2 -C 60 ) (g 1 -pip) 2 W(CO) 3 exclusively [3]. On the other hand, the observation that PPh 3 displaces C 60 from fac-(g 2 -C 60 )(g 2 -phen)W(CO) 3 is consistent with the strong cis-labilizing nature of phenanthroline [5,15]. We now report the results of the mechanistic study of the C 60 displacement from fac-(g 2 -C 60 )(g 2 -phen)Mo(CO) 3 by triphenylphosphine and tricyclohexyl phosphine in various solvents.…”