111464-90-5

Upstream product

• 79074-00-3 2,4,6-tri-t-butylphenylphosphonous dichloride 
• 480437-31-8 [Mo2(μ-H)(η5-cyclopentadienyl)2(PH(2,4,6-tBu3C6H2))(CO)4] 
• 201230-82-2 carbon monoxide 

Downstream Products

• 480437-35-2 [Mo2(η(5)-C5H5)2(CO)4(μ-H)(μ-P(CH2C(CH3)2)(C6H2(C(CH3)3)2))] 

Relevant academic research and scientific papers

Ten-Electron Coordination and Reactivity of an Arylphosphinidene Ligand

Photochemical decarbonylation of [Mo2Cp2(μ-PR*)(CO)4] (Cp = η5-C5H5; R* = 2,4,6-C6H2tBu3) gives [Mo2Cp2(μ-κ1:κ1,η6-PR*)(CO)2], which shows the first example of a remarkable 10-electron donor arylphosphinidene ligand which bridges two Mo atoms through its phosphorus atom while being π-bonded to one Mo center through the six carbon atoms of the aryl ring. This causes a severe pyramidal distortion of the P-bound C atom. The complex adds CO to give [Mo2Cp2(μ-κ1:κ1,η4-PR*)(CO)3], which has an 8-electron donor PR* ligand, and then the parent complex [Mo2Cp2(μ-PR*)(CO)4]. Protonation of [Mo2Cp2(μ-κ1:κ1,η6-PR*)(CO)2] gives the hydride [Mo2Cp2(H)(μ-κ1:κ1,η6-PR*)(CO)2]+, which undergoes P?C bond cleavage and hydride migration, affording the phosphido cation [Mo2Cp2(μ-P)(η6-R*H)(CO)2]+. Copyright

Formation and cleavage of P-C, Mo-C, and C-H bonds involving arylphosphinidene and cyclopentadienyl ligands at dimolybdenum centers

The phosphinidene-bridged complex [Mo2Cp2(μ -PR*)(CO)4] (R = 2,4,6- CoH2t Bu3) experiences an intramolecular C-H bond cleavage from a tBu group to give the phosphide-hydride derivative [Mo2-Cp2(μ-H) {μ-P(CH2CMe2)C6H2 tBu2}(CO)4] in refluxing diglyme (ca. 438 K) or under exposure to near-UV-visible light. In contrast, its exposure to UV light yields two different dicarbonyl derivatives depending on the reaction conditions, either the triply bonded [Mo2Cp2(μ- PR*)(μ-CO)2] (Mo-Mo = 2.5322(3) A) or its isomer [Mo2Cp2(μ-κ1:κ1, η6-PR*)(CO)2], in which the phosphinidene ligand bridges asymmetrically the metal centers while binding its aryl group to one of the molybdenum atoms in a η6-fashion. The latter complex experiences a proton-catalyzed tautomerization to yield the cyclopentadienylidene-phosphinidene derivative [Mo2Cp(μ- κ1:κ1, η5-PC5H 4)(η6-R*H)(CO)2]. Carbonylation of the η6-phosphinidene complex proceeds stepwise through the η4-tricarbonyl complex [Mo2Cp2(μ- κ1:κ1,η4-PR*)(CO) 3] and then to the starting tetracarbonyl compound, whereas its reaction with CNtBu yields only the η4-complex [Mo2Cp2(μ-κ1:κ1, η4-PR*)(CNtBu)(CO)2], which was characterized through an X-ray study. The η4-tricarbonyl species reacts with CNtBu in tetrahydrofuran to give the metal-metal bonded derivative [Mo2Cp2(μ-PR*)(CNtBu)(CO) 3]. In petroleum ether, however, this reaction yields the bis(isocyanide) derivative [Mo2Cp2(μ-PR*)(CN tBu)2(CO)3], which has an asymmetric trigonal phosphinidene bridge and no metal-metal bond. All the above results can be explained by assuming the operation of two primary processes in the photolysis of [Mo2Cp2(μ-PR*)(CO)4], one of them involving a valence tautomerization of the phosphinidene ligand, from the trigonal (four-electron donor) to the pyramidal (two-electron donor) coordination mode. The carbonylation reaction of the η6-complex is accelerated by the presence of CuCl, due to the formation of the trimetal species [CuMo2(Cl)Cp2(μ-κ1: κ1:κ1, η6-PR*)(CO) 2] and [CuMo2(Cl)-Cp2(μ-κ1: κ1:κ1,η4-PR*)(CO) 3]. The latter complexes were also characterized by single-crystal X-ray studies.

Proton induced P-H and Mo-H bond activation at the phosphide bridged dimolybdenum complexes [Mo2Cp2(μ-H)(μ-PHR)(CO) 4] (R = Cy, 2,4,6-C6H2R′3; R′ = H, Me, tBu)

The new hydride complexes [Mo2Cp2(μ-PHR)(CO) 4] having bulky substituents (R = 2,4,6-C6H 21Bu3 = Mes*, R = 2,4,6-C 6H2Me3 = Mes) have been prepared in good yield by addition of Li[PHR] to the triply bonded [Mo2Cp 2(CO)4] and further protonation of the resulting anionic phosphide complex [Mo2Cp2(μ-PHR)(CO)4] -. Protonation of the Mes* compound with either [H(OEt 2)2][B{3,5-C6H3(CF3) 2}4] or HBF4·OEt2 gives the cationic phosphinidene complex [Mo2Cp2(μ-H) (u-PMes*)(CO)4]+ in high yield. In contrast, protonation of the analogous hydride compounds with Mes or Cy substituents on phosphorus give the corresponding unsaturated tetracarbonyls [Mo2Cp 2(μ-PHR)(CO)4]+, which are unstable at room temperature and display a cis geometry. Decomposition of the latter give the electron-precise pentacarbonyls [Mo2Cp2(μ-PHR)(μ-CO) (CO)4]+, also displaying a cis arrangement of the metal fragments. In the presence of BF4- as external anion, fluoride abstraction competes with carbonylation to yield the neutral fluorophosphide hydrides [Mo2Cp2(μ-H)(μ-PFR)(CO) 4]. Similar results were obtained in the protonation reactions of the hydride compounds having a Ph substituent on phosphorus. In that case, using HCl as protonation reagent gave the chloro-complex [Mo,ClCp2(μ- PHPh)(CO)4] in good yield. The structures and dynamic behaviour of the new compounds are analyzed on the basis of solution IR and 1H, 31P, 19F and 13C NMR data as well as the X-ray studies carried out on [Mo2Cp2(μ-H)(μ-PHMes)(CO) 4] (cis isomer), [Mo2Cp2(μ-H)(μ-PFMes) (CO)4] (trans isomer), [Mo2Cp2(μ-PHCy)(μ- CO)(CO)4](BF4) and [Mo2ClCp2(μ- PHPh)(CO)4].

High yield synthesis and reactivity of a phosphinidene bridged dimolybdenum complex

Protonation of [Mo2Cp2(μ-H)(μ-PHR*)(CO)4] (Cp = η5-C5H5, R* = 2,4,6-C6H2tBu3) with HBF4·OEt2 gives the hydridophosphinidene complex [Mo2Cp2(μ-H)(μ-PR*)(CO)4]BF4, which is easily deprotonated with H2O to give the known phosphinidene complex [Mo2Cp2(μ-PR*)(CO)4] in 95% yield. Reaction of the latter with I2 gives the unsaturated phosphinidene complex [Mo2Cp2I2(μ-PR*)(CO)2], which exhibits an intermetallic distance of 2.960(2) A. Irradiation of solutions of [Mo2Cp2(μ-PR*)(CO)4] with UV light gives a mixture of the triply bonded [Mo2Cp2(μ-PR*)(μ-CO)2] and the hydridophosphido derivative [Mo2Cp2(μ-H){μ-P(CH2CMe2)C6H2tBu2}(CO)4] as major species. The latter complex results from an intramolecular C-H bond cleavage from a tBu group and has been characterized by spectroscopy and an X-ray study. Irradiation in the presence of HC≡C(p-tol) results in the insertion of the alkyne into the Mo-P bond to give [Mo2Cp2{μ-η1:η2,κ-C(p-tol)CHPR*}(CO)4] structurally characterized through an X-ray study. Copyright

Transition-metal phosphinidene complexes: Syntheses, structures, and bonding in dinuclear phosphinidene complexes containing 14- and 15-electron metal fragments

The reaction of Ar′PCl2 (Ar′ = 2,4,6-(t-Bu)3C6H2) with [Co(CO)4]- produces the dicobalt-phosphinidene complex [Co2(CO)6(μ-PAr′)] (1), which has been characterized by X-ray crystallography. Similar reactions between Ar′PCl2 and K[Mo(CO)3(η-C5H5)] and Na2[V(CO)3(η-C5H5)] afford the phosphinidene complexes [Mo2(CO)4(η-C5H5) 2(μ-PAr′)] (4) and [V2(CO)4(η-C5H5) 2(μ-PAr′)] (7). Reaction of the phosphine (TMP)PCl2 (TMP = 2,2,2′,2′-tetramethylpiperidino) with K[M(CO)3(η-C5H5)] (M = Mo, W) also affords the phosphinidene complexes [M2(CO)4(η-C5H5) 2{μ-P(TMP)}] [5 (M = Mo) and 6 (M = W)]. Compounds 4, 6, and 7 have been characterized by X-ray crystallography. Full details of the syntheses of the above compounds are presented together with a discussion of the structures and a theoretical (EHMO) study of the bonding and electronic properties.

Three-membered Ring featuring Metal-Phosphorus Multiple Bonding

The reaction of ArPCl2 (Ar = 2,4,6-t-Bu3C6H2) with K or K affords novel three-membered ring systems with metal-phosphorus bonding.