73985-32-7

Upstream product

• 12146-37-1 (bicyclo[2.2.1]hepta-2,5-diene)tetracarbonylmolybdenum⁽⁰⁾ 
• 638-21-1 phenylphosphane 
• 113754-21-5 {(CO)4Mo(PH₂CH₂CH₂C₅H₄N)(PH₂C₆H₅)} 
• 65337-26-0 bis(piperidyl)tetracarbonylmolybdenum⁽⁰⁾ 

Relevant academic research and scientific papers

Synthesis, spectroscopic and structural characterisation of chromium(0), molybdenum(0) and tungsten(0) complexes involving primary and secondary phosphines

[M(CO)6] (M=Mo or W) reacts with 4.5 molar equivalents of L (L=PPh2H or PPhH2) in excess ethanolic NaBH4 to yield the fac-trisubstituted species [M(CO)3(L)3] in good yield, with no evidence

Substitution of chloride in [PtCl2(dppe)] by the chiral anionic ligand [Mo(CO)5(PPhH)]-: Synthesis and X-ray structure of [Pt(μ-PPhH)2{Mo(CO)5}2(dppe)] and a 31P{1H} NMR analysis of its isomeric products and fluxionality

Reaction of the chiral anionic ligand [Mo(CO)5(PPhH)]- with [PtCl2(L-L)] affords the neutral trimetallic monophosphido bridged complexes [Pt(μ-PPhH)2{Mo-(CO)5}2(L-L)] (L-L = dppe, Ph2PCH2CH2PPh2, 2; dpae, Ph2AsCH2CH2AsPh2, 3; dppe′, cis-Ph2PCH=CHPPh2, 4). Compounds 2-4 are the first examples of heterometallic complexes that contain two chiral primary phosphido bridges existing as pairs of diastereoisomers. [Pt(μ-PPhH)2{Mo(CO)5}2(dppe)] (2) has been characterized spectroscopically and by a single-crystal X-ray analysis. The molecular structure of 2 can be considered either as Mo2Pt phosphido-bridged trimer or a square-planar PtII complex bonded to one chelating dppe and two anionic phosphine ligands. The latter PtP4 description successfully accounts for the line broadening observed in the 31P{1H} NMR spectra of 2-4, which can be understood in terms of the existence of several interconverting rotameric forms arising from restricted rotation about the Pt-phosphido bond. The Pt - P - Mo angles of 122.1(1) and 123.5(1)° are some of the largest ever to be reported for phosphido-bridged heterometallics, reflecting the long Pt - Mo separations [4.349(2) and 4.320(2) A] and the electronic and structural flexibility of the phosphido bridge. The PtMo compound [Pt(μ-PPhH)2{Mo-(CO)4}(dppe)] (5), comprised of one neutral and one dianionic chelate ligand, was prepared from [Li]2[Mo(CO)5(PPhH)2] and [PtCl2(dppe)] and was shown to contain a conformationally rigid PtP4 structure with characteristically sharp 31P resonances. The 31P{1H} NMR spectrum of 5 is rich with information analysing as two overlapping AA′XX′ spin systems together with their AA′XX′M (M = 195Pt) counterparts. The values of 2J(P - P) and 1J(195Pt - P) are significantly lower for PPhH{Mo(CO)5}- than dppe, a difference that cannot be accounted for solely on the basis of bond length variations. Meso-[Pt(μ-PPhH)2{Mo(CO)5}2(dppe)] (2) is thermodynamically unstable, undergoing a rapid intramolecular elimination of [Mo(CO)6] to generate [Pt(μ-PPhH)2{Mo(CO)4}(dppe)] (5), while its racemic diastereoisomer, that which was observed in the crystal, decomposes to unidentified phosphorus-containing products.

PH-Functional Phosphanes with 2-Pyridyl Substituents in α- or β-Position 2-C5H4N-n-PRH (R = H, iPr, tBu, Ph, 2-C5H4N-n; n = 1, 2)

PH-functional phosphanes containing a 2-pyridyl substituent in α- or β-position to phosphorus, e.g. 2-C5H4N-n-PRH (R = H, iPr, tBu, Ph; n = 1, 2) have been obtained.The reactivity of the PH-groups can be employed for the synthesis of tridentate NPN-hybrid donors, 2PR (R = H, Ph).The phosphanes 2-C5H4N-n-PRH behave as monodentate ligands in transition metal complexes and form labile chelate ring systems.They may bridge metal-metal bonds to form seven membered ring systems, e.g.Mo2PC3N.The coordination of the N-donor of the ligands 2-C5H4N- n-PRH to a transition metal atom is indicated by a lowfield shift and a small (31)P-(13)C-splitting of the 13C NMR signal of carbon atom 6 in the pyridin ring system. - 2-Pyridyl Substituent, Reactions at PH-Functions, Chelate Complexes, Ligand Replacement, 13C NMR Spectra