Carbon monoxide–phosphaalkyne coupling and C–H activation of an N–Me group in the 4e-η2-phosphaalkyne complex [WF(C6H4CH2NMeCH2CH2 NMe2)(CO)(η2-PCBut)]. Crystal and molecular structure of [WF{CH2N(CH2Ph)CH2CH2NMe 2}(CO){η4-PCBut(CO)CBu tP}]

Organometallic Fluorides: Compounds Containing Carbon−Metal−Fluorine Fragments of d-Block Metals

“…Although 235 is not isolable in crystalline form, further reaction with Bu t CtP affords 236, containing an η 2 -ligated 3,4-diphosphacyclopentadieneone group and a three-membered NCH 2 W ring system. 200 This behaviour is different to that of the η 2 -ligated nitrile complex whose chemistry is dominated by ready dissociation of the nitrile ligand. Generation of surface tethered tungsten(II) species (Figure 8) has been achieved by two routes.…”

“…It has been suggested that formation of 198 involves loss of one alkyne, with two successive protonations of the remaining alkynyl ligand to give the alkylidyne group followed by fluorination of the metal. 180,181 The fluoro hydride (MeCp)WF(H)(dmpe) (200) has been isolated as an unexpected product in the LiAlH 4 reduction of [(MeCp)W(dmpe)][PF 6 ]. Compound 200 has essentially a four-legged piano stool geometry with the chelating dmpe ligand spanning two trans sites and a terminal W-F distance of 2.04 Å.…”

Synthesis and Reactivity of the Phosphorus Analogues of Cyclopentadienone, Tricyclopentanone, and Housene

“…[3] To date,only one thermally stable,all-carbon housene E (X = CH 2 ,R = tBu, R' = CO 2 tBu) [4,5] has been reported. Incorporation of heteroatoms such as phosphorus into these molecules is appealing owing to their propensity to accommodate small angles and at the same time provide ac oordi-nation site.Sofar,studies on the phosphorus analogues of A-F are scarce, [6] and only Cowleysdiphosphatricyclopentanone G, [7] Nixonst riphospha analogue of housene H, [8] and Sekiguchism onophosphahousene I [9] have been reported.…”

Synthesis and Reactivity of the Phosphorus Analogues of Cyclopentadienone, Tricyclopentanone, and Housene

“…[13] Diphosphetanedione 3 is stable under an inert atmosphere,but is light-sensitive.Indaylight, it slowly releases CO, while irradiation with ax enon lamp quantitatively converts ab right yellow toluene solution of 3 into the orange diphosphene 4 (3 h, RT), which was isolated after removal of all volatiles in 99 %y ield (Scheme 3; d 31 P{ 1 H} = 585.3 ppm). [16,17] Them olecular structure of 4,d etermined by as ingle-crystal X-ray structure determination (Figure 1, top left), [18] reveals ac entrosymmetric diphosphene with typical P1ÀP1a (2.0210 (6) )and P1ÀC1 (1.8778(12) )bond lengths and a syn conformation (P1a-P1-C1-C4 171.67(4)8 8)of the cyclopropenyl groups and the P = Pdouble bond. Note that the related bis(pentamethylcyclopentadienyl)diphosphene (Cp*P=PCp*) has the cyclopentadienyl rings and P=Pb ond positioned anti to each other.…”