Preparation and reactivity of mononuclear platinum(0) complexes containing a η2-coordinated alkynylphosphine

Bennett, Martin A.; Kwan, Laurence C. H.; Rae, A. David; Wenger, Eric; Willis, Anthony C.

doi:10.1039/b107015k

Cited by 29 publications

(29 citation statements)

References 41 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…4,29 As expected, there is a marked deviation from linearity in the diynyl fragment upon coordination with bend back angles at C a and C b that are very acute (134.6(5) and 144.0(6) • , respectively). This is indicative of some metallacyclopropene character to the bonding and also consistent with back-bonding from Pt(2) into the p*(C≡C) • ).…”

supporting

confidence: 67%

“…Transition metal complexes containing alkynyl phosphines (PPh 2 C≡CR) display a fascinating chemistry and have been widely investigated. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16] Although diynylphosphine ligands may offer higher coordination possibilities and new reaction paths they have, however, been less explored. The diynylphosphines PPh 2 C≡CXC≡CR are also potential building blocks to build new polymetallic complexes with interesting structural and material properties.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Synthesis and characterization of mono- and binuclear platinum complexes containing terminal and bridging diynyldiphenylphosphine ligands

et al. 2004

View full text Add to dashboard Cite

A series of mononuclear platinum complexes containing diynyldiphenylphosphine ligands [cis-Pt(C(6)F(5))(2)(PPh(2)C[triple bond]CC(6)H(4)C[triple bond]CR)L](n)(n= 0, L = tht, R = Ph 2a, Bu(t)2b; L = PPh(2)C[triple bond]CC(6)H(4)C[triple bond]CR, 4a, 4b; n=-1, L = CN(-), 3a, 3b) has been synthesized and the X-ray crystal structures of 4a and 4b have been determined. In order to compare the eta2-bonding capability of the inner and outer alkyne units, the reactivity of towards [cis-Pt(C(6)F(5))(2)(thf)(2)] or [Pt(eta2)-C(2)H(4))(PPh(3))(2)] has been examined. Complexes coordinate the fragment "cis-Pt(C(6)F(5))(2)" using the inner alkynyl fragment and the sulfur of the tht ligand giving rise the binuclear derivatives [(C(6)F(5))(2)Pt(mu-tht)(mu-1kappaP:2eta2-C(alpha),C(beta)-PPh(2)C[triple bond]CC(6)H(4)C[triple bond]CR)Pt(C(6)F(5))(2)](R = Ph 5a, Bu(t)5b). The phenyldiynylphosphine complexes 2a, 3a and 4a react with [Pt(eta2)-C(2)H(4))(PPh(3))(2)] to give the mixed-valence Pt(II)-Pt(0) complexes [((C(6)F(5))(2)LPt(mu-1kappaP:2eta2)-C(5),C(6)-PPh(2)C[triple bond]CC(6)H(4)C[triple bond]CPh))Pt(PPh(3))(2)](n)(L = tht 6a, CN 8a and PPh(2)C[triple bond]CC(6)H(4)C[triple bond]CPh 9a) in which the Pt(0) fragment is eta2-complexed by the outer fragment. Complex 6a isomerizes in solution to a final complex [((C(6)F(5))(2)(tht)Pt(mu-1kappaP:2eta2)-C(alpha),C(beta)-PPh(2)C[triple bond]CC(6)H(4)C[triple bond]CPh))Pt(PPh(3))(2)]7a having the Pt(0) fragment coordinated to the inner alkyne function. In contrast, the tert-butyldiynylphosphine complexes 2b and 3b coordinate the Pt(0) unit through the phosphorus substituted inner acetylenic entity yielding 7b and 8b. By using 4a and 2 equiv. of [Pt(eta2)-C(2)H(4))(PPh(3))(2)] as precursors, the synthesis of the trinuclear complex [cis-((C(6)F(5))(2)Pt(mu-1kappaP:2eta2)-C(5),C(6)-PPh(2)C[triple bond]CC(6)H(4)C[triple bond]CPh)(2))(Pt(PPh(3))(2))(2)]10a, bearing two Pt(0)(PPh(3))(2)eta2)-coordinated to the outer alkyne functions is achieved. The structure of 7a has been confirmed by single-crystal X-ray diffraction.

show abstract

supporting

confidence: 67%

Section: Introductionmentioning

confidence: 99%

Synthesis and characterization of mono- and binuclear platinum complexes containing terminal and bridging diynyldiphenylphosphine ligands

et al. 2004

View full text Add to dashboard Cite

show abstract

“…Complex 10 represents to our knowledge one of the few examples of an allene complex formed from the isomerization of an alkyne ligand in the coordination sphere of platinum. 13 …”

Section: Resultsmentioning

confidence: 99%

Bite-angle bending as a key for understanding group-10 metal reactivity of d¹⁰-[M(NHC)₂] complexes with sterically modest NHC ligands

et al. 2015

View full text Add to dashboard Cite

show abstract

“…35 X-ray quality crystals were obtained from a benzene/hexane solution of 7 at −20 °C, thus allowing for a comparison of the geometric features of the alkyne versus carbyne moieties (Figure 2). 36 The P(CCPh)Ph moiety is oriented such that the phenyl group eclipses one carbonyl ligand, while the CCPh group bisects the N31−W1−C2(O) angle (Figure 2 inset). This differs from the PPh 2 conformation in 2a, in which the two phenyl groups eclipse one carbonyl ligand and one pyrazolyl ring.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Chlorophosphino Carbyne Complexes of Tungsten

Colebatch

Hill

2016

Organometallics

View full text Add to dashboard Cite

A range of chlorophosphinocarbyne complexes [W(CPClR)(CO) 2 (Tp*)] (R = Cl, Cy, Ph; Tp* = hydrotris-(3,5-dimethylpyrazol-1-yl)borate) has been prepared by reaction of chlorophosphines with the lithiocarbyne complex [W{ CLi(THF) n }(CO) 2 (Tp*)]. These complexes undergo nucleophilic substitution of chloride to enable the preparation of phosphinocarbynes bearing alkyl, aryl, alkynyl, aryloxy, and secondary phosphino substituents [W(CPRR′)(CO) 2 (Tp*)] (R = Ph, R′ = Me, Ph, CCPh, OPh, H; R = Cy, R′ = H). ■ INTRODUCTIONCarbynes L n MCR, as one of the simplest carbon-based ligands, and phosphines, as ubiquitous (spectator and noninnocent) ligands, both represent in their own way fundamental groups in organometallic chemistry. Despite dating back to Fischer's seminal report in 1973, 1 the appearance of carbyne complexes in the literature remains somewhat sporadic. A notable exception to this involves carbyne complexes serving as catalysts for alkyne metathesis, which continues to receive considerable attention. 2−8 Carbyne complexes bearing heteroatom carbyne substituents have been less studied, and in part this reflects limitations in synthetic methodologies that are typically distinct from classical Fischer or Schrock protocols. 9−16 We have enjoyed some success employing the "M-(CO) 2 (Tp*)" fragments (M = Mo, W; Tp* = 3,5-hydrotris-(dimethylpyrazolyl)borate)) for the construction of comparatively elaborate carbyne complexes, in particular those that bear heteroatomic carbyne subsitutents. 17−29 The combination of the bulky Tp* ligand (Tolman cone angle = 224°), 30 which affords kinetic stabilization, and the π-acidic CO coligands, which render the metal center relatively inert, allows modifications at the carbyne ligand to proceed, in many cases, without disruption of the MC linkage or M-(CO) 2 (Tp*) coordination sphere. In contrast to carbyne chemistry, phosphorus chemistry is very mature. Chlorophosphines are the quintessential building blocks for a myriad of phosphorus species due to the high reactivity of the P−Cl linkage and subsequent ease of nucleophilic substitution at this position.Combining these two principles we have considered the marriage of conventional organophosphorus chemistry with that of carbyne complexes. We have previously demonstrated that tertiary phosphinocarbyne complexes [M(CPPh 2 )-(CO) 2 (Tp*)] (M = W 2a, Mo 2b)) 21,29 and phosphonito carbynes [Mo{CP(O)(OEt) 2 }(CO) 2 (Tp*)] 21 are readily accessible from the bromocarbyne precursor [M(CBr)-(CO) 2 (Tp*)] (M = W 1a, Mo 1b) via lithium/halogen exchange with n BuLi and nucleophilic substitution of PClPh 2 or alternatively via palladium-catalyzed phosphination using PH-(O)(OEt) 2 , respectively. These complexes possess relatively inert phosphorus centers, undergoing conventional "phosphinetype" reactions with electrophiles, oxidants, and metal centers.In search of more versatile precursors, it has been found that the palladium-mediated protocol is also effective for the preparation of secondary phosphinocarbynes [W(CPHR)-(CO) 2 (Tp...

show abstract

Preparation and reactivity of mononuclear platinum(0) complexes containing a η2-coordinated alkynylphosphine

Cited by 29 publications

References 41 publications

Synthesis and characterization of mono- and binuclear platinum complexes containing terminal and bridging diynyldiphenylphosphine ligands

Synthesis and characterization of mono- and binuclear platinum complexes containing terminal and bridging diynyldiphenylphosphine ligands

Bite-angle bending as a key for understanding group-10 metal reactivity of d¹⁰-[M(NHC)₂] complexes with sterically modest NHC ligands

Chlorophosphino Carbyne Complexes of Tungsten

Contact Info

Product

Resources

About

Preparation and reactivity of mononuclear platinum(0) complexes containing a η2-coordinated alkynylphosphine

Cited by 29 publications

References 41 publications

Synthesis and characterization of mono- and binuclear platinum complexes containing terminal and bridging diynyldiphenylphosphine ligands

Synthesis and characterization of mono- and binuclear platinum complexes containing terminal and bridging diynyldiphenylphosphine ligands

Bite-angle bending as a key for understanding group-10 metal reactivity of d10-[M(NHC)2] complexes with sterically modest NHC ligands

Chlorophosphino Carbyne Complexes of Tungsten

Contact Info

Product

Resources

About

Bite-angle bending as a key for understanding group-10 metal reactivity of d¹⁰-[M(NHC)₂] complexes with sterically modest NHC ligands