Phosphenium complexes 30. Supermesitylphosphenium complexes of molybdenum and tungsten: synthesis and exchange reactions involving the PH bond

Malisch, Wolfgang; Hirth, Ulrich-Andreas; Grün, Klaus; Schmeußer, Martin

doi:10.1016/s0022-328x(98)00947-4

Cited by 15 publications

(13 citation statements)

References 25 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Spectroscopic data in solution for 3 and 3′ are similar to each other (Table ) and consistent with the solid-state structure of the molybdenum anion, and otherwise might be related to the structure of the neutral chlorophosphide complexes [MCp(PClR*)(CO) 2 ] [M = Mo, W] . The anionic nature of complexes 3 and 3′ , however, causes a significant reduction in the two C−O stretching frequencies of the carbonyl groups, as expected.…”

Section: Resultssupporting

confidence: 80%

Chemistry of the Oxophosphinidene Ligand. 1. Electronic Structure of the Anionic Complexes [MCp{P(O)R}(CO)₂]⁻(M = Mo, W; R = 2,4,6-C₆H₂^tBu₃) and Their Reactions with H⁺and C-Based Electrophiles.

et al. 2010

View full text Add to dashboard Cite

The anionic phosphide-bridged complexes (H-DBU)[M(2)Cp(2)(μ-PHR*)(CO)(4)] (M = Mo, W; R* = 2,4,6-C(6)H(2)(t)Bu(3); Cp = η(5)-C(5)H(5), DBU = 1,8-diazabicyclo [5.4.0] undec-7-ene) react with molecular oxygen to give the corresponding oxophosphinidene complexes (H-DBU)[MCp{P(O)R*}(CO)(2)] as major products (Mo-P = 2.239(1) Å for the Mo complex). The latter anionic complexes are protonated by HBF(4)·OEt(2) to give the hydroxyphosphide derivatives [MCp{P(OH)R*}(CO)(2)]. In the presence of excess acid, the molybdenum complex yields the fluorophosphide complex [MoCp(PFR*)(CO)(2)] (Mo-P = 2.204(1) Å), while the tungsten compound reacts with excess HCl to give an unstable chlorophosphine complex [WCpCl(PHClR*)(CO)(2)] which is rapidly hydrolyzed to give [WCpCl{PH(OH)R*}(CO)(2)], having a complexed arylphosphinous acid (Mo-P = 2.460(2) Å). The molybdenum anion reacts with strong C-based electrophiles such as [Me(3)O]BF(4), Et(2)SO(4), C(2)H(3)C(O)Cl, and PhC(O)Cl to give the corresponding alkoxyphosphide derivatives [MoCp{P(OR)R*}(CO)(2)] (R = Me, Et, COC(2)H(3), COPh; Mo-P = 2.197(2) Å for the benzoyl compound), as a result of the attack of the electrophile at the O atom of the oxophosphinidene ligand. In contrast, the reactions with milder alkylating reagents such as the alkyl halides MeI, EtI, C(3)H(5)Br, and C(3)H(3)Br give selectively the corresponding κ(2)-phosphinite complexes [MoCp{κ(2)-OP(R)R*}(CO)(2)] [R = Me, Et, C(3)H(5), C(3)H(3); Mo-P = 2.3733(5) Å for the allyl compound] as a result of the attack of the electrophile at the P atom of the oxophosphinidene ligand. According to density functional theory (DFT) calculations, the oxygen atom of the phosphinidene ligand bears the highest negative charge in the molybdenum anion, while the highest occupied molecular orbital (HOMO) of this complex has substantial Mo-P π bonding character. Thus, it is concluded that the phosphinite complexes are formed under conditions of orbital control, while charge-controlled reactions tend to give alkoxyphosphide derivatives.

show abstract

Section: Resultssupporting

confidence: 80%

Chemistry of the Oxophosphinidene Ligand. 1. Electronic Structure of the Anionic Complexes [MCp{P(O)R}(CO)₂]⁻(M = Mo, W; R = 2,4,6-C₆H₂^tBu₃) and Their Reactions with H⁺and C-Based Electrophiles.

et al. 2010

View full text Add to dashboard Cite

show abstract

“…The structure of this molecule is similar to that of the alkoxyphosphide 2c , displaying a quite short MoP distance [2.2037(12) Å] (Figure ) . Compound 3 appears to be the first complex reported with a trigonal fluorophosphide (PFR) ligand, although a few related chlorophosphide complexes are known 2 Molecular structure of compounds 3 (left) and 4b (right).…”

supporting

confidence: 87%

Chemistry of the Phosphinidene Oxide Ligand

et al. 2004

View full text Add to dashboard Cite

Reaction of [Mo2Cp2(mu-H)(mu-PHR*)(CO)4] with DBU followed by O2 gives the first anionic phosphinidene oxide complex (H-DBU)[MoCp{P(O)R*}(CO)2] (1) (DBU = 1,8-diazabicyclo [5.4.0] undec-7-ene; R* = 2,4,6-C6H2tBu3). This anion displays three different nucleophilic sites located at the O, P, and Mo atoms, as illustrated by the reactions reported. Thus, reaction of 1 with excess HBF4.OEt2 gave the fluorophosphide complex [MoCp(PFR*)(CO)2] via the hidroxophosphide intermediate [MoCp{PR*(OH)}(CO)2]. Related alkoxyphosphide compounds [MoCp{P(OR)R*}(CO)2] (R = Me, C(O)Ph) were prepared by reaction of 1 with [Me3O]BF4 and PhC(O)Cl, respectively, whereas reaction of 1 with MeI or C3H5Br gave the P,O-bound phosphinite complexes [MoCp(kappa2-OPRR*)(CO)2] (R = Me, C3H5). Metal-based electrophiles were found to bind at either O or Mo positions. Thus, reaction of 1 with [ZrCl2Cp2] gave the phosphinidene oxide bridged [MoCp{P(OZrClCp2)R*}(CO)2], whereas reaction with SnPh3Cl gave trans-[MoCp{P(O)R*}(CO)2(SnPh3)], an heterometallic complex having an intact terminal P(O)R* ligand.

show abstract

“…As for the formation of 4, the synthetic procedure used here is similar to that reported by Malisch to convert the anti isomer of compound 1 into anti-4. 11 The syn conformation of the Cp and R* groups in 4 has been verified both in solution and through an X-ray study of the complex (see the Supporting Information, SI). As expected, 4 displays a quite short Mo−P length of 2.2212(8) Å, only slightly longer than the one determined for its fluorophosphanyl analogue [2.204(1) Å].…”

mentioning

confidence: 85%

“…We note that this procedure also works efficiently by using Mn instead of Re. As for the formation of 4 , the synthetic procedure used here is similar to that reported by Malisch to convert the anti isomer of compound 1 into anti - 4 . The syn conformation of the Cp and R* groups in 4 has been verified both in solution and through an X-ray study of the complex (see the Supporting Information, SI).…”

mentioning

confidence: 88%

Efficient Synthesis and Multisite Reactivity of a Phosphinidene-Bridged Mo–Re Complex. A Platform Combining Nucleophilic and Electrophilic Features

et al. 2020

View full text Add to dashboard Cite

The heterometallic complex [MoReCp(μ-PR*)(CO) 6 ] (3) was prepared in 60% overall yield from syn-[MoCp(PHR*)(CO) 2 ] via a three-step procedure involving complexes syn-[MoCp(PClR*)(CO) 2 ] and [MoReCp(μ-PR*)(CO) 7 ] as intermediate species (R* = 2,4,6-C 6 H 2 t Bu 3 ). The PR* ligand in 3 displays a novel asymmetric interaction with the dimetal center, involving a double bond with one atom (Mo) and a dative single bond with the other one (Re). Compound 3 underwent thermal isomerization involving a C−H bond cleavage to yield the hydride [MoReCp(μ-H){μ-P(CH 2 CMe 2 )C 6 H 2 t Bu 2 }(CO) 6 ] and reacted with I 2 to give [MoReCpI 2 (μ-PR*)(CO) 6 ], which displays a symmetrical phosphinidene bridge. Its reaction with methyl propiolate at 293 K proceeded with [2 + 2] cycloaddition of the alkyne and decarbonylation to yield the phosphapropenylidene-bridged complex [MoReCp{μ-κ 2 P,C :η 3 -PR*CHC(CO 2 Me)}(CO) 5 ] as the major product, whereas its reaction with excess CN(4-C 6 H 4 OMe) at 273 K proceeded with formal [2 + 1] cycloaddition of the isocyanide and further isocyanide addition at the Re site to yield the complex [MoReCp{μ-η 2 P,C :κ 1 P -PR*CN(4-C 6 H 4 OMe)}(CO) 6 {CN(4-C 6 H 4 OMe)}], which displays an azaphosphaallene ligand in a novel bridging coordination mode.

show abstract

Phosphenium complexes 30. Supermesitylphosphenium complexes of molybdenum and tungsten: synthesis and exchange reactions involving the PH bond

Cited by 15 publications

References 25 publications

Chemistry of the Oxophosphinidene Ligand. 1. Electronic Structure of the Anionic Complexes [MCp{P(O)R}(CO)₂]⁻(M = Mo, W; R = 2,4,6-C₆H₂^tBu₃) and Their Reactions with H⁺and C-Based Electrophiles.

Chemistry of the Oxophosphinidene Ligand. 1. Electronic Structure of the Anionic Complexes [MCp{P(O)R}(CO)₂]⁻(M = Mo, W; R = 2,4,6-C₆H₂^tBu₃) and Their Reactions with H⁺and C-Based Electrophiles.

Chemistry of the Phosphinidene Oxide Ligand

Efficient Synthesis and Multisite Reactivity of a Phosphinidene-Bridged Mo–Re Complex. A Platform Combining Nucleophilic and Electrophilic Features

Contact Info

Product

Resources

About

Phosphenium complexes 30. Supermesitylphosphenium complexes of molybdenum and tungsten: synthesis and exchange reactions involving the PH bond

Cited by 15 publications

References 25 publications

Chemistry of the Oxophosphinidene Ligand. 1. Electronic Structure of the Anionic Complexes [MCp{P(O)R*}(CO)2]−(M = Mo, W; R* = 2,4,6-C6H2tBu3) and Their Reactions with H+and C-Based Electrophiles.

Chemistry of the Oxophosphinidene Ligand. 1. Electronic Structure of the Anionic Complexes [MCp{P(O)R*}(CO)2]−(M = Mo, W; R* = 2,4,6-C6H2tBu3) and Their Reactions with H+and C-Based Electrophiles.

Chemistry of the Phosphinidene Oxide Ligand

Efficient Synthesis and Multisite Reactivity of a Phosphinidene-Bridged Mo–Re Complex. A Platform Combining Nucleophilic and Electrophilic Features

Contact Info

Product

Resources

About

Chemistry of the Oxophosphinidene Ligand. 1. Electronic Structure of the Anionic Complexes [MCp{P(O)R}(CO)₂]⁻(M = Mo, W; R = 2,4,6-C₆H₂^tBu₃) and Their Reactions with H⁺and C-Based Electrophiles.

Chemistry of the Oxophosphinidene Ligand. 1. Electronic Structure of the Anionic Complexes [MCp{P(O)R}(CO)₂]⁻(M = Mo, W; R = 2,4,6-C₆H₂^tBu₃) and Their Reactions with H⁺and C-Based Electrophiles.