Is the phosphaethynolate anion, (OCP)−, an ambident nucleophile? A spectroscopic and computational study

Heift, Dominikus; Benkő, Zoltán; Grützmacher, Hansjörg

doi:10.1039/c3dt53569j

Cited by 102 publications

(129 citation statements)

References 40 publications

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“…The global minimum 28-1S (C 2h ) has two three-electron donor bridging phosphaketenyl m-PCO ligands bonded to the manganese atoms solely through the phosphorus atoms. The geometry of 28-1S is similar to H 2 Mn 2 (CO) 8 predicted in a previous DFT study, 29 and also similar to H 2 Re 2 (CO) 8 observed by X-ray crystallography. 30,31 The C 2v structure 28-2S, lying only 0.4 kcal mol À1 (B3LYP or BP86) in energy above 28-1S, is a cis stereoisomer with different PCO orientations.…”

Section: Resultssupporting

confidence: 76%

Carbonyl migration from phosphorus to the metal in binuclear phosphaketenyl metal carbonyl complexes to give bridging diphosphido complexes

et al. 2015

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Alkali metal salts of the 2-phosphaethynolate anion PCO À synthesized from reactions of CO with NaPH 2 or K 3 P 7 have recently become available in quantities for the synthesis of transition metal complexes of the potentially ambidentate PCO ligand (Angew. Chem., Int. Ed., 2013, 38, 10064). This is exemplified by the recently reported rhenium carbonyl complex (triphos)Re(CO) 2 (PCO) (triphos = MeP(CH 2 PPh 2 ) 3 ). Density functional theory studies on the related manganese carbonyl complexes Mn(CO) n (PCO) (n = 5, 4, 3) andMn 2 (CO) n (PCO) 2 (n = 8, 7, 6, 5) are now reported. For the binuclear systems the low-energy Mn 2 (CO) 8 (PCO) 2 structures are singlet spin state structures having two bridging P-bonded phosphaketenyl m-PCO ligands without a direct Mn-Mn bond. Carbonyl loss from Mn 2 (CO) 8 (m-PCO) 2 is predicted to lead to migration of CO groups from phosphorus to manganese resulting in Mn 2 (CO) n+2 (m-P 2 ) structures with bridging diphosphido groups as the lowest energy Mn 2 (CO) n (PCO) 2 isomers (n = 7, 6, 5). Isomeric Mn 2 (CO) 6 (PCO) 2 structures with dihapto bridging Z 2 -m-PCO ligands at B30 kcal mol À1 above the global minimum are also found representing intermediates in the migration of CO groups from phosphorus to manganese. For the mononuclear systems the P-bonded Mn(CO) n (PCO) (n = 5, 4) phosphaketenyl structures are found to lie 20 to 28 kcal mol À1 in energy below the isomeric O-bonded Mn(CO) n (PCO) phosphaethynoxy isomers consistent with previously reported results by Grützmacher and coworkers on R 3 E(PCO)-R 3 E(OCP) systems (R = iPr, Ph; E = Si, Sn, Ge, Pb). The lowest energy structure for the tricarbonyl Mn(CO) 3 (PCO) is a singlet structure with an unusual trihapto Z 3 -PCO ligand. However, higher energy isomeric Mn(CO) 3 (PCO) structures with P-bonded phosphaketenyl or O-bonded phosphaethynoxy ligands and tetrahedral Mn coordination are also found.

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Section: Resultssupporting

confidence: 76%

Carbonyl migration from phosphorus to the metal in binuclear phosphaketenyl metal carbonyl complexes to give bridging diphosphido complexes

et al. 2015

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“…The observed spectra for HPCO deviate significantly from the known anion PCO − , for which δ( 31 P)=−396.8 and δ( 13 C)=170.3 ppm ( 1 J C‐P =62 Hz) was recorded,41 but are well within the broad range of shifts observed for known phosphaketenes [for example, (DippNCH 2 ) 2 P−PCO: δ( 31 P)=−232.6 ppm (d, 1 J P‐P =252.5 Hz);42 [E]−PCO (E=Re, Co, Cu, Au, Si‐Ge: −200.2 to −397.5 ppm],43, 44, 45, 46, 47, 48 and related species ([U]/[Th]−OCP: −334, −285 ppm) 49. The chemical shifts also bear resemblance to known R 2 CPH species for which a considerable dependence on solvent polarity was also observed for the δ( 1 H) shift [R 2 C= Dipp NHC: δ( 31 P)=−136.7, δ( 1 H)=1.92, 1 J P‐H =164 Hz; R 2 C= Ar* NHC: δ( 31 P)=−134.5, δ( 1 H)=2.10, 1 J P‐H =172 Hz; R 2 C=various NHC from Ref.…”

supporting

confidence: 72%

HPCO—A Phosphorus‐Containing Analogue of Isocyanic Acid

et al. 2017

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We describe the isolation and spectroscopic characterization of the heavier phosphorus‐containing analogue of isocyanic acid (HPCO), and its isotopologue (DPCO). This fundamental small molecule, which has been postulated to exist in interstellar space, has thus far only been observed at low gas phase concentrations or in inert gas matrices. In this report we describe its synthesis, spectroscopic properties, and reactivity in solution.

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“…TheG e À P distances of 2.4762 (5) and 2.4775(5) a re significantly longer than that calculated for Ge-P single bond in Ph 3 GeÀ P=C=O( 2.398 , at the B3LYP/cc-pVDZ(-PP) level). [8] In contrast, the PÀCd istances of 1.643 (2) and 1.639(2) a re shorter than the calculated values for Ph 3 Ge-P = C = O (1.684 ), while the C À Ob ond distances (1.166 (3) and 1.170(3) ) are comparable to that of Ph 3 Ge-P = C = O (1.165 ).…”

contrasting

confidence: 46%

“…[8] No evidence for the presence of the corresponding phosphaethynolato germylene isomer (LGeÀOÀC P) could be observed both in the solid state (IR spectroscopy) Scheme 1. Synthesis of the phosphaketenyl-substituted germylenes 2a and 2b from the corresponding chlorogermylenes 1a and 1b,r espectively.…”

mentioning

confidence: 96%

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From a Phosphaketenyl‐Functionalized Germylene to 1,3‐Digerma‐2,4‐diphosphacyclobutadiene

et al. 2016

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Molecules bearing multiple bonds between two heavier main-group elements are often elusive intermediates.B y taking advantage of kinetic and/or thermodynamic stabilization strategies,s uch highly reactive species can nevertheless be turned into classes of compounds that are isolable. [1] In this context, heteronuclear multiple bonds between the heavier Group 14 and 15 elements have attracted much attention owing to their unique reactivity and electronic properties. [1,2] After the successful synthesis of an isolable Si=Pc ompound reported by Bickelhaupt and co-worker in 1984, [3] several striking examples featuring multiply bonded heavier Group 14 and 15 elements have been isolated and structurally characterized. [1][2][3][4][5] However,the synthesis of more unsaturated triply bonded REP(E= Si, Ge) species remains challenging because of the even higher tendency of EPbonds to undergo dimerization or oligomerization.Recently,w hen we attempted to synthesize as table SiÀP triply bonded compound, aphosphasilyne [LSi P],wecould only isolate its corresponding head-to-tail dimer,t he 4p-electron resonance-stabilized 2,4-disila-1,3-diphosphacyclobutadiene.[4k] Herein, we wish to report the unexpectedly facile access to the first head-to-tail dimer of ap hosphagermyne,s tarting from an ovel phosphaketenyl-functionalized germylene.F urthermore,a nu nprecedented N,P-heterocyclic bis-germylene could be synthesized via ar emarkable and unexpected condensation reaction.At first, the N-heterocyclic [6] were allowed to react with one molar equivalent of sodium phosphaethynolate,ac onvenient anionic phosphorus atom transfer reagent for which as ynthesis was recently developed, [7] to give the phosphaketenyl germylenes 2a and 2b,r espectively,i n quantitative yield according to 1 Hand 31 PNMR spectroscopy (Scheme 1). Both were isolated as yellow crystals in 90 and 92 %y ields,r espectively.T heir constitutions and compositions were proved by 1 H, 13 C, 31 PNMR spectroscopy,e lemental analyses and high resolution-mass spectrometry (HR-MS) (see the Supporting Information).The 31 PNMR spectrum of 2a and 2b shows as inglet at d = À298.9 and À304.9 ppm, respectively.B oth resonances are shifted to higher frequencies compared to Ph 3 Ge-P=C=O (d = À344.0 ppm).[8] TheI Rs pectra of 2a and 2b exhibit intense stretching vibrations at ñ = 1895 and 1887 cm À1 , respectively,f or the PCO groups (Ph 3 Ge À P = C = O: ñ = 1954 cm À1 ). [8] No evidence for the presence of the corresponding phosphaethynolato germylene isomer (LGeÀOÀC P) could be observed both in the solid state (IR spectroscopy) Scheme 1. Synthesis of the phosphaketenyl-substituted germylenes 2a and 2b from the corresponding chlorogermylenes 1a and 1b,r espectively.[

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Is the phosphaethynolate anion, (OCP)−, an ambident nucleophile? A spectroscopic and computational study

Cited by 102 publications

References 40 publications

Carbonyl migration from phosphorus to the metal in binuclear phosphaketenyl metal carbonyl complexes to give bridging diphosphido complexes

Carbonyl migration from phosphorus to the metal in binuclear phosphaketenyl metal carbonyl complexes to give bridging diphosphido complexes

HPCO—A Phosphorus‐Containing Analogue of Isocyanic Acid

From a Phosphaketenyl‐Functionalized Germylene to 1,3‐Digerma‐2,4‐diphosphacyclobutadiene

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