Experimental and Computational Studies on the Formation of Thorium–Copper Heterobimetallics

Yang, Pikun; Zhou, Enwei; Hou, Guohua; Zi, Guofu; Ding, Wanjian; Walter, Marc D.

doi:10.1002/chem.201603519

Cited by 63 publications

(55 citation statements)

References 134 publications

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“…For example,( C 5 Me 5 ) 2 [( i Pr)NC(Me)N( i Pr)]Th(Me) has thoriumnitrogen bond distances of 2.509(2) and 2.515 (2) . [39] TheTh À P2 and ThÀNb onds are 2.982(2) and 2.106(5) ,r espectively.T he ThÀNl ength is only slightly longer than metallocene complexes with thorium-nitrogen (imido) bond distances of 2.091(7) and 2.045(8) in (C 5 Me 5 ) 2 Th[=N(Mes)](DMAP), [46] DMAP = 4-(dimethylamino)pyridine,a nd (C 5 Me 5 ) 2 Th[ = N-(Mes)](THF). [49] Given previous results of deprotonating phosphido ligands to produce aterminal thorium phosphinidene using ab ase and 2,2,2-cryptand, [50,51] we attempted deprotonation with complex 1,E quation (2).…”

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“…There is only one example of ap roton-bound phosphaamidinate previously reported. [44] TheT h-P2 (phosphido) bond of 2.9377(11) in 1 is similar to the 2.9406 (11) in (Tren DMBS )AnP-(SiMe 3 ) 2 , [45] while the Th-P1 distance is slightly longer at 3.0085 (12) .A ne longation in the Th À Nb ond is also observed at 2.444(4) which is longer than most Th À N(primary amide) bonds.F or example,(C 5 Me 5 ) 2 Th[NH-(Mes)] 2 [46] and (1,2,4-t BuC 6 H 2 ) 2 Th[NH-p-tolyl)] 2 [47] have ThÀ Nd istances of 2.344(12) and 2.283(3) ,r espectively.H owever,t his bond distance is reasonable for a k 2 -ligand. For example,( C 5 Me 5 ) 2 [( i Pr)NC(Me)N( i Pr)]Th(Me) has thoriumnitrogen bond distances of 2.509(2) and 2.515 (2) .…”

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confidence: 99%

“…Thed eprotonation of the amide produces adianionic aza-1-phosphaallyl ligand, [k 1 -N = C( t Bu)P(Mes)] 2À .Again, only one example of this moiety has been reported, but with m 2 :k 2 coordination. [39] TheTh À P2 and ThÀNb onds are 2.982(2) and 2.106(5) ,r espectively.T he ThÀNl ength is only slightly longer than metallocene complexes with thorium-nitrogen (imido) bond distances of 2.091(7) and 2.045 (8) in (C 5 Me 5 ) 2 Th[=N(Mes)](DMAP), [46] DMAP = 4-(dimethylamino)pyridine,a nd (C 5 Me 5 ) 2 Th[ = N-(Mes)](THF). [52] TheN À Cb ond is 1.340(7) while the…”

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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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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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“…16 More recent examples of thorium-transition metal complexes include combinations with cobalt 10 and copper. 17 …”

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Uranium rhodium bonding in heterometallic complexes

et al. 2017

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“…[2][3][4][5] Thed iscovery of as table compound with fivefold chromium-chromium (Cr À Cr) bonding in 2005 [6] revived efforts to synthesize and characterize homoas well as hetero-metal-metal bonding compounds across the periodic table from the d-block transition metals to the fblock lanthanides and actinides. [7][8][9][10][11][12] Metal-metal bonding of f-block actinide elements is of particular interest in understanding of the electronic structures,e specially f-orbital participation. Theb onding scenario of actinide elements such as uranium is considerably more complex than that in the d-block metals because the 5f,6 d, 7s,a nd 7p orbitals are energetically close to one another,and thus,all are available in forming the chemical bonds.D espite the proclivity of multiply bonded metal-containing complexes to exhibit novel types of bonding and reactivity,c omplexes containing actinide-metal bonds are uncommon largely due to the extreme difficulties in experimental synthesis and characterization.…”

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Preparation and Characterization of Uranium–Iron Triple‐Bonded UFe(CO)₃⁻ and OUFe(CO)₃⁻ Complexes

Chi

Wang

et al. 2017

Angewandte Chemie

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We report the preparation of UFe(CO) 3 À and OUFe(CO) 3 À complexes using alaser-vaporization supersonic ion source in the gas phase.T hese compounds were massselected and characterized by infrared photodissociation spectroscopya nd state-of-the-art quantum chemical studies. There are unprecedented triple bonds between U6d/5fa nd Fe 3d orbitals,featuring one covalent s bond and two Fe-to-U dative p bonds in both complexes.T he uranium and iron elements are found to exist in unique formal U(I or III) and Fe(ÀII) oxidation states,r espectively.T hese findings suggest that there may exist aw hole family of stable df-d multiplebonded f-element-transition-metal compounds that have not been fully recognized to date.

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Experimental and Computational Studies on the Formation of Thorium–Copper Heterobimetallics

Cited by 63 publications

References 134 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

Uranium rhodium bonding in heterometallic complexes

Preparation and Characterization of Uranium–Iron Triple‐Bonded UFe(CO)₃⁻ and OUFe(CO)₃⁻ Complexes

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Experimental and Computational Studies on the Formation of Thorium–Copper Heterobimetallics

Cited by 63 publications

References 134 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

Uranium rhodium bonding in heterometallic complexes

Preparation and Characterization of Uranium–Iron Triple‐Bonded UFe(CO)3− and OUFe(CO)3− Complexes

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Preparation and Characterization of Uranium–Iron Triple‐Bonded UFe(CO)₃⁻ and OUFe(CO)₃⁻ Complexes