P–H bond activation at a tungsten(0) centre: synthesis and characterisation of WH(PPh2)(dppe)2

Field, Leslie D.; Jones, Neale G.; Turner, Peter

doi:10.1016/s0022-328x(98)00693-7

Cited by 6 publications

(5 citation statements)

References 16 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…No trans -PH 2 –Fe–H coupling is observed, similar to the comparative complex trans -[W(H)(PPh 2 ) 2 (dppe) 2 ] reported by Field and co-worker where only the coupling from the hydride to dppe was observed as a pentet . It has been noted trans -R 2 P–M–H geometries are rare and indeed only a handful have been characterized extensively. ,,, Complex 9 displays an Fe1–H1 distance of 1.48(4) Å and an Fe1–P5 distance of 2.337(1) Å. In comparison and as expected, Scheer’s bridged iron species displays much shorter Fe–P bond distances (Fe1–P1 2.2159 Å and Fe1–P2 2.2205 Å), which is in line with the bridging environment of the phosphide in that complex.…”

Section: Results and Discussionsupporting

confidence: 74%

“… 69 It has been noted trans -R 2 P–M–H geometries are rare and indeed only a handful have been characterized extensively. 51 , 69 , 70 , 71 Complex 9 displays an Fe1–H1 distance of 1.48(4) Å and an Fe1–P5 distance of 2.337(1) Å. In comparison and as expected, Scheer’s bridged iron species displays much shorter Fe–P bond distances (Fe1–P1 2.2159 Å and Fe1–P2 2.2205 Å), 34 which is in line with the bridging environment of the phosphide in that complex.…”

Section: Results and Discussionmentioning

confidence: 99%

See 1 more Smart Citation

Synthesis and Characterization of a Terminal Iron(II)–PH₂ Complex and a Series of Iron(II)–PH₃ Complexes

Lau,

Mahon,

Webster

2024

Inorg. Chem.

View full text Add to dashboard Cite

Reported is the reaction of a series of iron(II) bisphosphine complexes with PH 3 in the presence of NaBAr F 4 [where BAr F 4 = tetrakis(3,5-bis(trifluoromethyl)phenyl)borate]. The iron-(II) bisphosphine reagents bear two chlorides or a hydride and a chloride motif. We have isolated six different cationic terminal-bound PH 3 complexes and undertaken rigorous characterization by NMR spectroscopy, single crystal X-ray diffraction, and mass spectrometry, where the PH 3 often remains intact during the ionization process. Unusual bis-and tris-PH 3 complexes are among the compounds isolated. Changing the monophosphine from PH 3 to PMe 3 results in the formation of an unusual Fe 7 cluster, but with no PMe 3 being ligated. Finally, by using an iron(0) source, we have provided a rare example of a terminally bound iron−PH 2 complex.

show abstract

Section: Results and Discussionsupporting

confidence: 74%

Section: Results and Discussionmentioning

confidence: 99%

Synthesis and Characterization of a Terminal Iron(II)–PH₂ Complex and a Series of Iron(II)–PH₃ Complexes

Lau,

Mahon,

Webster

2024

Inorg. Chem.

View full text Add to dashboard Cite

show abstract

“…In contrast, W–P double bonds are usually much shorter (2.28 Å) . The P(2)–W(3) bond [2.5274(8) Å] is longer than the other W–P bonds in complex 2c , but still in the range of literature values .…”

Section: Resultsmentioning

confidence: 84%

Unusual Reactivity of cyclo‐(P₅Ph₅): Oxidative Addition at a Group 6 Metal Carbonyl and Insertion of Acetonitrile into a P–P Bond

2019

View full text Add to dashboard Cite

The reaction of [M(CO) 4 L x ] {M = Cr, W, L = MeCN, x = 2; M = Mo, L = 2,5-norbornadiene (nbd), x = 1} with cyclo-(P 5 Ph 5 ) led to an unusual transformation reaction including the oxidative addition of a P-P bond to the Group 6 metal carbonyl, the insertion of MeCN into a P-P bond, and the formation of an M-M bond. The products were characterized by IR and 31 P{ 1 H} NMR spectroscopy, ESI mass spectrometry and single

show abstract

“…Hydrido‐phosphanido complexes of early and middle transition metals have also been prepared from oxidative addition reactions of the coordinatively and electronically unsaturated complex [Ta( t Bu 3 SiO) 3 ], and also from electronically saturated complexes [Mo(Cp*)(Cl)(N 2 )(PMe 3 ) 2 ], and [W(dppe) 2 (N 2 ) 2 ] with HPPh 2 . The later require light irradiation to dissociate dinitrogen and thus generate the required coordination vacancy.…”

Section: Introductionmentioning

confidence: 99%

“…This undesirable situation can be avoided by using bulky ligands, as observed in the reaction of [Co(dtbpe)(C 2 H 4 )] (dtbpe = 1,2-bis(ditert-butylphosphano)ethane) with 2,6-dimesitylphenylphosphane (DmpPH 2 ), which gives [Co(dtbpe)(H)(PHDmp)]. [22] Hydrido-phosphanido complexes of early and middle transition metalsh avea lso been prepared from oxidative addition reactions of the coordinatively and electronicallyu nsaturated complex [Ta(tBu 3 SiO) 3 ], [23] and also from electronically saturated complexes [Mo(Cp*)(Cl)(N 2 )(PMe 3 ) 2 ], [24] and [W(dppe) 2 (N 2 ) 2 ] [25] with HPPh 2 .T he later require light irradiation to dissociate dinitrogen and thus generatethe required coordination vacancy.…”

Section: Introductionmentioning

confidence: 99%

Rhodium Complexes in P−H Bond Activation Reactions

Varela‐Izquierdo

Geer

Bruin

et al. 2019

Chemistry A European J

View full text Add to dashboard Cite

The feasibility of oxidative addition of the P−H bond of PHPh2 to a series of rhodium complexes to give mononuclear hydrido‐phosphanido complexes has been analyzed. Three main scenarios have been found depending on the nature of the L ligand added to [Rh(Tp)(C2H4)(PHPh2)] (Tp= hydridotris(pyrazolyl)borate): i) clean and quantitative reactions to terminal hydrido‐phosphanido complexes [RhTp(H)(PPh2)(L)] (L=PMe3, PMe2Ph and PHPh2), ii) equilibria between RhI and RhIII species: [RhTp(H)(PPh2)(L)]⇄[RhTp(PHPh2)(L)] (L=PMePh2, PPh3) and iii) a simple ethylene replacement to give the rhodium(I) complexes [Rh(κ2‐Tp)(L)(PHPh2)] (L=NHCs‐type ligands). The position of the P−H oxidative addition–reductive elimination equilibrium is mainly determined by sterics influencing the entropy contribution of the reaction. When ethylene was used as a ligand, the unique rhodaphosphacyclobutane complex [Rh(Tp)(η1‐Et)(κC,P‐CH2CH2PPh2)] was obtained. DFT calculations revealed that the reaction proceeds through the rate limiting oxidative addition of the P−H bond, followed by a low‐barrier sequence of reaction steps involving ethylene insertion into the Rh−H and Rh−P bonds. In addition, oxidative addition of the P−H bond in OPHPh2 to [Rh(Tp)(C2H4)(PHPh2)] gave the related hydride complex [RhTp(H)(PHPh2)(POPh2)], but ethyl complexes resulted from hydride insertion into the Rh−ethylene bond in the reaction with [Rh(Tp)(C2H4)2].

show abstract

P–H bond activation at a tungsten(0) centre: synthesis and characterisation of WH(PPh2)(dppe)2

Cited by 6 publications

References 16 publications

Synthesis and Characterization of a Terminal Iron(II)–PH₂ Complex and a Series of Iron(II)–PH₃ Complexes

Synthesis and Characterization of a Terminal Iron(II)–PH₂ Complex and a Series of Iron(II)–PH₃ Complexes

Unusual Reactivity of cyclo‐(P₅Ph₅): Oxidative Addition at a Group 6 Metal Carbonyl and Insertion of Acetonitrile into a P–P Bond

Rhodium Complexes in P−H Bond Activation Reactions

Contact Info

Product

Resources

About

P–H bond activation at a tungsten(0) centre: synthesis and characterisation of WH(PPh2)(dppe)2

Cited by 6 publications

References 16 publications

Synthesis and Characterization of a Terminal Iron(II)–PH2 Complex and a Series of Iron(II)–PH3 Complexes

Synthesis and Characterization of a Terminal Iron(II)–PH2 Complex and a Series of Iron(II)–PH3 Complexes

Unusual Reactivity of cyclo‐(P5Ph5): Oxidative Addition at a Group 6 Metal Carbonyl and Insertion of Acetonitrile into a P–P Bond

Rhodium Complexes in P−H Bond Activation Reactions

Contact Info

Product

Resources

About

Synthesis and Characterization of a Terminal Iron(II)–PH₂ Complex and a Series of Iron(II)–PH₃ Complexes

Synthesis and Characterization of a Terminal Iron(II)–PH₂ Complex and a Series of Iron(II)–PH₃ Complexes

Unusual Reactivity of cyclo‐(P₅Ph₅): Oxidative Addition at a Group 6 Metal Carbonyl and Insertion of Acetonitrile into a P–P Bond