[(CO)₄W(PH₃)₂] as a Source of Semi-interstitial Phosphorus Ligands in Cobalt Carbonyl Clusters

Abstract

The PH 3 -containing complex [(CO) 4 W(PH 3 ) 2 ] (1) is synthesized in good yields by the "one-pot" reaction of [(CO) 4 W(nbd)] (nbd = norbonadiene) with P(SiMe 3 ) 3 and subsequent methanolysis of the reaction mixture. The further reaction of [(CO) 4 W(PH 3 ) 2 ] with [Co 2 (CO) 8 ] results in three novel cobalt clusters, [Co 8 (CO) 18 ( μ 6 -P) 2 ( μ-CO)] (2), [Co 10 (CO) 18 ( μ 7 -P) 2 ( μ-CO) 6 ] (3), and [[Co 3 (CO) 8 -{μ 4 -PW(CO) 5 }][( μ 4 -P)Co 3 (CO) 9 ]] (4). All products have been comprehensively characterized including X-ray diffraction.

Transition metal complexes of the naked pnictide elements

“…18 The cluster Co3(CO)9PCo3(CO)8PW(CO)5 ( Figure 25) shows a coupled set of spiked tetrahedral species. 43 Both cluster cores are derived from Co3(CO)9P units, which has long been known and is highly reactive leading spontaneously to the cyclic trimer [Co3(CO)8P]3. Cyclization is hindered by providing an additional metal for complexation of the P lone pair.…”

“…[73][74][75] W(CO)4(PH3)2 can also serve as a source of P atoms in reaction with cobalt carbonyl. 43 A common structural unit seen within these clusters is the Co6P unit in which a PCo4 square pyramid is capped on two PCo2 faces by additional Co atoms. This is most simply illustrated by Co6(CO)12(PS2C3H6)(S2C3H6)(µ6-P) ( Figure 49D) 74 and Co6((CO)10(PS2C3H6)(S2C3H6)-({P(OEt)3}2(µ6-P) ( Figure 48E).…”

“…This is most simply illustrated by Co6(CO)12(PS2C3H6)(S2C3H6)(µ6-P) ( Figure 49D) 74 and Co6((CO)10(PS2C3H6)(S2C3H6)-({P(OEt)3}2(µ6-P) ( Figure 48E). 74 Figure 49A) 73 can be viewed as having two of these units fused along a Co-Co edge, while Co8(CO)19(µ7-P)2 ( Figure 49B) 43 shows two of these units fused along the Co4 face. The latter can alternately be viewed as a P2Co4 octahedron with four faces capped by Co groups.…”

“…The latter can alternately be viewed as a P2Co4 octahedron with four faces capped by Co groups. Compound Co10(CO)24(µ7-P)2 ( Figure 49C) 43 also has a distorted central P2Co4 octahedron, but two PCo2 faces are capped with Co3. The [Co9(CO)21(µ9-P)] 2ion ( Figure 49F)\ 75 shows a monocapped square antiprism of cobalt atoms with an interstitial phosphide atom, while addition of Co(CO)4to that compound led to the isolation of [Co10(CO)22(µ8-P)] 3- (Figure 49G), which shows a bicapped square antiprism core.…”

Stoichiometry-controlled FeP nanoparticles synthesized from a single source precursor

“…Taking advantage of our expertise in metal pnictides, 21 we have recently reported the synthesis of [(CO) 4 W(PH 3 ) 2 ] by the ''one-pot'' reaction of [(CO) 4 W(nbd)] (nbd = norbornadiene) with P(SiMe 3 ) 3 and subsequent methanolysis of the reaction mixture. 22 The advantages of this synthetic route are good yields and that use of PH 3 is avoided. We have successfully transferred this concept to the formation of 1 (see ESI † for X-ray structure) which was obtained in excellent yields using the same route as that previously described for [(CO) 4 W(PH 3 ) 2 ] (eqn (1)…”