Borylcarbyne Complexes: [Mo(≡CBR2)(CO)2{HB(pzMe2)3}] (BR2= B(NMe2)2, BO2C6H4; pz = pyrazol-1-yl)

Hill, Anthony F.; Shang, Rong; Willis, Anthony C.

doi:10.1021/om200261h

Cited by 19 publications

(3 citation statements)

References 68 publications

(35 reference statements)

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“…In these conversions, the labile {B}−Cl fragments are prone to afford neutral derivatives. 432 For example, BCl(NMe 2 ) 2 , BCl(cat), and BCl(OMe 433 In terms of reactivity, [(Tp′)(OC) 2 MC−Li] (M = Mo, W) complexes show parallels to acetylides. For instance, SnClBu 3 provides access to the stannyl-functionalized carbide, [(Tp′)-(OC) 2 WC−SnBu 3 ], which engages in Stille coupling reactions with pyridyl, 434 bipyridyl, 435 and (polycyclic) aryl 436 halides as substrates (Figure 81).…”

Section: T H Imentioning

confidence: 99%

Transition Metal Carbide Complexes

Reinholdt

Bendix

2021

Chem. Rev.

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Carbide complexes remain a rare class of molecules. Their paucity does not reflect exceptional instability but is rather due to the generally narrow scope of synthetic procedures for constructing carbide complexes. The preparation of carbide complexes typically revolves around generating L n M−CE x fragments, followed by cleavage of the C−E bonds of the coordinated carbon-based ligands (the alternative being direct C atom transfer). Prime examples involve deoxygenation of carbonyl ligands and deprotonation of methyl ligands, but several other p-block fragments can be cleaved off to afford carbide ligands. This Review outlines synthetic strategies toward terminal carbide complexes, bridging carbide complexes, as well as carbide−carbonyl cluster complexes. It then surveys the reactivity of carbide complexes, covering stoichiometric reactions where the carbide ligands act as C 1 reagents, engage in cross-coupling reactions, and enact Fischer−Tropsch-like chemistry; in addition, we discuss carbide complexes in the context of catalysis. Finally, we examine spectroscopic features of carbide complexes, which helps to establish the presence of the carbide functionality and address its electronic structure.

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Section: T H Imentioning

confidence: 99%

Transition Metal Carbide Complexes

Reinholdt

Bendix

2021

Chem. Rev.

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“…107 Boryl carbyne complexes have also been reported in 2011. 108 A review describing the most recent advances in acyclic boron containing p-ligands has been published. 109 The coordination chemistry of Group 13 monohalides (including BX units) has been reviewed in 2011.…”

Section: Heteroboranesmentioning

confidence: 99%

Boron, aluminium, gallium, indium and thallium

Johnson¹

2012

Annu. Rep. Prog. Chem., Sect. A: Inorg. Chem.

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“…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. − The combination of the bulky Tp* ligand (Tolman cone angle = 224°), 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.…”

Section: Introductionmentioning

confidence: 99%

Chlorophosphino Carbyne Complexes of Tungsten

Colebatch

Hill

2016

Organometallics

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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...

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Borylcarbyne Complexes: [Mo(≡CBR₂)(CO)₂{HB(pzMe₂)₃}] (BR₂= B(NMe₂)₂, BO₂C₆H₄; pz = pyrazol-1-yl)

Cited by 19 publications

References 68 publications

Transition Metal Carbide Complexes

Transition Metal Carbide Complexes

Boron, aluminium, gallium, indium and thallium

Chlorophosphino Carbyne Complexes of Tungsten

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