Complete Hydrogen Transfer: Tin Hydride Reactivity toward Adamantylisonitrile and Benzonitrile

Aicher, Frederik S. W.; Eichele, Klaus; Schubert, Hartmut; Wesemann, Lars

doi:10.1021/acs.organomet.8b00207

Cited by 12 publications

(12 citation statements)

References 91 publications

(143 reference statements)

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“…Throughout the Fischer–Tropsch reaction chemistry literature, we cannot find any report in which a proton is transferred directly to the carbon of CO without an external agent (Lewis acid or proton source) or beginning from a hydride source. Proton transfer reactions to CO or substrates isoelectronic with CO (such as isocyanides) are known in organometallic chemistry, these usually involve metal‐hydride precursors, addition of a protonic substrate, electrophile addition, or ligand degradation . Other examples involving Frustrated Lewis Pairs (FLPs) have been noted, but we can find no prior reports of unassisted functionalization of CO (other than when hydride is part of the starting material).…”

Section: Figurementioning

confidence: 99%

Functionalization of Carbon Monoxide and tert‐Butyl Nitrile by Intramolecular Proton Transfer in a Bis(Phosphido) Thorium Complex

et al. 2018

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We report intramolecular proton transfer reactions to functionalize carbon monoxide and tert‐butyl nitrile from a bis(phosphido) thorium complex. The reaction of (C5Me5)2Th[PH(Mes)]2, Mes=2,4,6‐Me3C6H2, with 1 atm of CO yields (C5Me5)2Th(κ2‐(O,O)‐OCH2PMes‐C(O)PMes), in which one CO molecule is inserted into each thorium–phosphorus bond. Concomitant transfer of two protons, formerly coordinated to phosphorus, are now bound to one of the carbon atoms from one of the inserted CO molecules. DFT calculations were employed to determine the lowest energy pathway. With tert‐butyl nitrile, tBuCN, only one nitrile inserts into a thorium–phosphorus bond, but the proton is transferred to nitrogen with one phosphido remaining unperturbed affording (C5Me5)2Th[PH(Mes)][κ2‐(P,N)‐N(H)C(CMe3)P(Mes)]. Surprisingly, reaction of this compound with KN(SiMe3)2 removes the proton bound to nitrogen, not phosphorus.

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Section: Figurementioning

confidence: 99%

Functionalization of Carbon Monoxide and tert‐Butyl Nitrile by Intramolecular Proton Transfer in a Bis(Phosphido) Thorium Complex

et al. 2018

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“…Hydride chemistry of the heavy group 14 elements has recently attracted many research groups. Whereas tributyltin hydride is a well-known reagent in organic transformations, recent hydride chemistry of germanium and tin is focused on reactivity studies of low-valent hydride derivatives. − After publication of the first low-valent tin hydride stabilized by a bulky organic substituent in 2000 a variety of low-valent hydrides of germanium and tin have been published. ,− These hydrides are very reactive compounds, which exhibit hydroelementation reactions, activation of small molecules, and were shown to act as catalysts in organic transformation reactions. − In the past, we have studied the reductive elimination of hydrogen to synthesize low-valent hydrides of tin starting from organotin trihydrides. − In reaction with N-heterocyclic carbenes (NHC), NHC adducts of low-valent tin hydrides and with diethylmethylamine donor-free organotin hydrides were synthesized in high yield.…”

Section: Introductionmentioning

confidence: 99%

Deprotonation of Organogermanium and Organotin Trihydrides

et al. 2019

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Terphenyltin and terphenylgermanium trihydrides were deprotonated in reaction with strong bases, such as LiMe, LDA, or KBn. In the solid state, the Li salts of the germate anion 4 and 4a exhibit a Li–Ge contact. In the Li salt of the dihydridostannate anion 6a, the Li cation is not coordinated at the tin atom instead an interaction of the Li cation with the hydride substituents was found. Evidenced by 1H–7Li-HOESY NMR spectroscopy the Li-salt of the deprotonated tin hydride 6a exhibits in toluene solution a contact between Li cation and hydride substituents, whereas in the 1H–7Li-HOESY NMR spectrum of the homologous germate salt 4a, no crosspeak between hydride and Li signals was found. The organodihydridogermate and -stannate react as nucleophiles with low-valent Group 14 electrophiles. Thus, three compounds were synthesized: Ar–Ë′–EH2–Ar (E′, E = Sn, Ge; Pb, Ge; Pb, Sn; Ar = Ar′, Ar*). Following an alternative synthesis Ar′SnH2PbAr* was synthesized in reaction between [(Ar*PbH)2] and [(Ar′SnH)4] generated in situ. In reaction between low-valent organotin hydride [(Ar*SnH)2] and organdihydridostannate [Ar*SnH2]− formation of distannate [Ar*2Sn2H3]− was found.

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“…[61,62] Throughout the Fischer-Tropsch reaction chemistry literature,w e cannot find any report in which ap roton is transferred directly to the carbon of CO without an external agent (Lewis acid or proton source) or beginning from ah ydride source. Proton transfer reactions to CO or substrates isoelectronic with CO (such as isocyanides) are known in organometallic chemistry,t hese usually involve metal-hydride precursors, [63][64][65][66][67][68] addition of ap rotonic substrate, [69] electrophile addition, [70] or ligand degradation. [71] Other examples involving Frustrated Lewis Pairs (FLPs) have been noted, [72][73][74] but we can find no prior reports of unassisted functionalization of CO (other than when hydride is part of the starting material).…”

Section: Angewandte Chemiementioning

confidence: 99%

Functionalization of Carbon Monoxide and tert‐Butyl Nitrile by Intramolecular Proton Transfer in a Bis(Phosphido) Thorium Complex

et al. 2018

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We report intramolecular proton transfer reactions to functionalize carbon monoxide and tert-butyl nitrile from ab is(phosphido) thorium complex. The reaction of (C 5 Me 5 ) 2 Th[PH(Mes)] 2 ,M es = 2,4,6-Me 3 C 6 H 2 ,w ith 1atm of CO yields (C 5 Me 5 ) 2 Th(k 2 -(O,O)-OCH 2 PMes-C(O)PMes),i n which one CO molecule is inserted into each thoriumphosphorus bond. Concomitant transfer of two protons, formerly coordinated to phosphorus,a re nowb ound to one of the carbon atoms from one of the inserted CO molecules. DFT calculations were employed to determine the lowest energy pathway. With tert-butyl nitrile, t BuCN,only one nitrile inserts into at horium-phosphorus bond, but the proton is transferred to nitrogen with one phosphido remaining unperturbed affording (C 5 Me 5 ) 2 Th[PH(Mes)][k 2 -(P,N)-N(H)C-(CMe 3 )P(Mes)].S urprisingly,r eaction of this compound with KN(SiMe 3 ) 2 removes the proton bound to nitrogen, not phosphorus.Carbon monoxide is aC 1 feedstock molecule with relatively inert chemistry owing to the strength of the CO bond. [1] The transformation of non-renewable products,s uch as CO and CO 2 ,i nto starting materials and value-added chemicals is desirable.T his has been accomplished for decades using Fischer-Tropsch chemistry in which CO and H 2 are converted into liquid hydrocarbons. [2] However,t his reaction requires acatalyst as well as elevated temperature and pressure.Thus, novel techniques for hydrogen addition to CO,i ncluding stoichiometric reactions,w ould enhance our knowledge of functionalizing CO into hydrocarbons.Mid-to late-transition metal carbonyl complexes are well known. In contrast, the actinides are large,h ighly electropositive metals with minimal metal-ligand bonding interaction, and their valence orbitals have little need for p-acceptor ligands.T herefore,C Oi sapoor ligand for felements,w ith few examples. [3][4][5][6][7][8][9] However,t hese characteristics make actinides well-suited for small molecule activation of oxygenated substrates. [10,11] While reductive coupling of CO is readily accomplished by low-valent f-element complexes such as U III , [12][13][14][15][16][17][18][19][20] Sm II , [21] and aL a III dinitrogen complex, [22] the most common reaction with CO is migratory insertion and CÀC bond formation. [23][24][25][26][27][28][29][30][31][32] However,t wo reports describe the reductive coupling of CO with U III complexes,a nd have observed proton migration to carbon, but only upon heating. [33,34] Our group has been exploring the unusual reactivity of actinide-phosphorus bonds to exploit hard-soft differences, [35] as well as the weak actinide-phosphorus bond which should be effective for small molecule activation. Thei nsertion of CO into at horium-, scandium, or hafnium-phosphorus bond has been previously reported. [36][37][38][39] Both of these reactions produce h 2 -acyl products.H erein, we report the reactivity of the bis(phosphido) complex, (C 5 Me 5 ) 2 Th[PH(Mes)] 2 , [40] Mes = 2,4,6-Me 3 C 6 H 2 ,w ith CO in which both protons are transferred from ph...

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Complete Hydrogen Transfer: Tin Hydride Reactivity toward Adamantylisonitrile and Benzonitrile

Cited by 12 publications

References 91 publications

Functionalization of Carbon Monoxide and tert‐Butyl Nitrile by Intramolecular Proton Transfer in a Bis(Phosphido) Thorium Complex

Functionalization of Carbon Monoxide and tert‐Butyl Nitrile by Intramolecular Proton Transfer in a Bis(Phosphido) Thorium Complex

Deprotonation of Organogermanium and Organotin Trihydrides

Functionalization of Carbon Monoxide and tert‐Butyl Nitrile by Intramolecular Proton Transfer in a Bis(Phosphido) Thorium Complex

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