Substituted boat-shaped Co6 carbonyl cluster derivatives containing a semi-interstitial P atom and both bridging dithiolate and heterocyclic phosphido ligands

Transformation of μ4-Phosphinidenes at an Ru5 Center: Isolation and Structural Characterization of Hydroxyphosphinidene Cluster Acids, Fluorophosphinidenes, and a Novel μ5-Phosphide

“…The resonance for the dppm ligand appears at δ 28.5 as a doublet. The long-range P-F coupling expected on the basis of the 19 F spectrum is masked by the broadness of the peaks in the 31 P spectrum.…”

“…7,10 Compound 7 can be readily characterized by IR and NMR. The PF ligand appears in the 19 F NMR spectrum as a doublet of triplets at δ 8.7, showing a large one-bond P-F coupling constant of 1076 Hz, as well as a long-range coupling constant of 20 Hz to the dppm phosphorus atoms. In the 31 P NMR spectrum, the PF ligand appears as a doublet of triplets at δ 539, showing the large one-bond P-F coupling constant, as well as a long-range P-P coupling constant of 31 Hz.…”

Transition metal complexes of the naked pnictide elements

“…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). 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.…”

“…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.…”

“…Reaction of cobalt carbonyl or cobalt carbonyl anions with a variety of phosphorus reagents can lead directly to the encapsulation of a naked P atom. [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.…”