Substitution reaction of triphenylphosphine oxide with rare-earth metal phosphido methyl complexes

Lv, Yingdong; Zhou, Jiafeng; Leng, Xuebing; Chen, Yaofeng

doi:10.1039/c5nj00335k

Cited by 13 publications

(13 citation statements)

References 16 publications

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“…Scandium methyl chloride compounds [LSc(Me)Cl] (L = [MeC(NDIPP)CHC(Me)NCH 2 CH 2 NMe 2 ] − ; DIPP = 2,6-( i Pr) 2 C 6 H 3 ) and BrB{N(DIPP)CHCHN(DIPP)}) were prepared as previously reported. , A salt metathesis of BrB{N(DIPP)CHCHN(DIPP)} with NaPH 2 in THF provided the boronylphosphine H 2 PB{N(DIPP)CHCHN(DIPP)} in 78% yield. The 31 P NMR spectrum of the compound in C 6 D 6 shows a diagnostic triplet at δ = −250.3 ppm (t, 1 J P–H = 198.2 Hz), being upfield shifted as compared to that of H 2 PP{N(DIPP)CH 2 CH 2 N(DIPP)} (δ = −157.6 ppm) .…”

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Scandium-Terminal Boronylphosphinidene Complex

Feng

Carpentier

et al. 2021

J. Am. Chem. Soc.

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The first isolation and structural characterization of a rare-earth metal-terminal imido complex were reported in 2010, but a rare-earth metal-terminal phosphinidene complex is still absent, to date. Herein, we report the synthesis and structure of the first example of a rare-earth-terminal phosphinidene complex, namely the scandium boronylphosphinidene complex. Single-crystal X-ray diffraction shows that the complex has a much shorter Sc−P bond length as compared to that in a related scandium boronylphosphido complex, 2.381(1) Å vs 2.564(1) Å. DFT calculations indicate the presence of a strong Sc−P π interaction in this complex, which is in striking contrast to the weak interaction found in the phosphido complex. A preliminary reactivity study demonstrates that the scandium-terminal boronylphosphinidene complex behaves as a nucleophilic phosphinidene complex.

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Scandium-Terminal Boronylphosphinidene Complex

Feng

Carpentier

et al. 2021

J. Am. Chem. Soc.

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“…Toluene, benzene, tetrahydrofuran, hexane, [D 6 ]benzene, and [D 8 ]THF were dried over Na/K alloy, transferred under vacuum, and stored in the glovebox. LiL (L=[MeC(NDIPP)CHC(Me)(NCH 2 CH 2 N(Me) 2 )] − , DIPP=2,6‐( i Pr) 2 C 6 H 3 ), Li[CH(SiMe 3 )PPh 2 S], Li[CH(SiMe 3 )PPh 2 S](THF), [LLu(Me)Cl], [LSc{C(SiR 3 )PPh 2 S}] (R=Me, Ph), and [L′Sc{C(SiR 3 )PPh 2 S}] (L′=[MeC(NDIPP)CHC(Me)(NCH 2 CH 2 N( i Pr) 2 )] − ; R=Me, Ph) were synthesized according to the reported procedures. Benzonitrile, tert ‐butyl isonitrile, and phenylsilane were dried over activated 4 Å molecular sieves and degassed by three freeze–pump–thaw cycles before use.…”

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confidence: 99%

“…Molecular structure of complex 20 with ellipsoidsat3 0% probability level. Selectedb ond lengths []and angles [8]: SmÀN1 2.4146(16), SmÀ N2 2.4089(16), SmÀN3 2.9873(5), SmÀN4 2.314(2), SmÀS2 .778(1),S m ÀP 2.987(1), N4ÀC22 1.323(2),C22ÀC23 1.219(3), SÀP2.060(1); Sm-N4-C22 97.06(12), N4-C22-C23 173.3(2),C22-C23-Si1 67.76(19), P-S-Sm 74.62(2).…”

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“…Molecular structure of complex 21 with ellipsoids at 30 %p robability level. DIPP isopropylg roups and hydrogen atoms were omitted for clarity.S elected bond lengths []a nd angles [8]: SmÀN1 2.359(3),Sm ÀN2 2.197(3), SmÀN3 2.649(3), SmÀC22 2.833(3), SmÀS2 .892(1), C2ÀC3 1.372(5), C3ÀC4 1.536(5);Sm-C22-Si1 86.14(12), Sm-C22-Si2 126.99(14), Sm-C22-P 90.08(14), Si1-C22-P 112.44(18), Si2-C22-P 124,46(19).…”

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Monomeric Rare‐Earth Metal Silyl‐Thiophosphinoyl‐Alkylidene Complexes: Synthesis, Structure, and Reactivity

Wang

Mao

et al. 2018

Chemistry A European J

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A series of monomeric rare-earth metal silyl-thiophosphinoyl-alkylidene complexes [LLn{C(SiR )PPh S}] (5: Ln=Lu, R=Me; 6: Ln=Lu, R=Ph; 7: Ln=Y, R=Me; 8: Ln=Y, R=Ph; 9: Ln=Sm, R=Ph; 10: Ln=Sm, R=Me; 11: Ln=La, R=Ph; L=[MeC(NDIPP)CHC(Me)(NCH CH N(Me) )] , DIPP=2,6-(iPr) C H ) have been synthesized and structurally characterized. The influences of rare-earth metal ions, ancillary ligands, and alkylidene groups on the reactivity of complexes 5-11 and the related scandium complexes [LSc{C(SiR )PPh S}] (1: R=Me; 2: R=Ph) and [L'Sc{C(SiR )PPh S}] (3: R=Me; 4: R=Ph; L'=[MeC(NDIPP)CHC(Me)(NCH CH N(iPr) )] ) have been studied. Reactions of these rare-earth metal alkylidene complexes with PhCN give four kinds of products, the formation of which is dependent on the rare-earth metal ions, ancillary ligands, and alkylidene groups of the complexes. In the reactions with tBuNC, unusual C-P bond cleavage of the alkylidene group and C≡C triple bond formation occur. Complexes 10 and 11 also react with PhSiH to form hydrides, which subsequently undergo Ln-H addition to the C=N bond of the ancillary ligand L. DFT calculations have been used to analyze the bonding in complex 10, which exhibits a polarized three centers Sm-C-P π interaction, and to rationalize the reactivity by computing reaction mechanisms. The difference in reactivity of PhCN and tBuNC is due to the electron density delocalization that is enabled by the phenyl group rather than the tBu group.

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“…This is rationalized by computational approaches and is due to the Lewis acidity of the metal center that binds tightly THF molecule. 24 , and [L′Sc(Me)Cl] (L′ = [MeC(NDIPP) CHC(Me)(NCH 2 CH 2 N(Me) 2 )] − ) 25 were prepared as reported. Phosphinophosphine H 2 PP{N(DIPP)CH 2 CH 2 N(DIPP)} was synthesized by a salt metathesis of ClP{N(DIPP)CH 2 CH 2 N (DIPP)} 26,27 with NaPH 2 in THF.…”

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Synthesis and versatile reactivity of scandium phosphinophosphinidene complexes

Feng

McCabe

et al. 2020

Nat Commun

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M=E/M≡E multiple bonds (M = transition metal, E = main group element) are of significant fundamental scientific importance and have widespread applications. Expanding the ranges of M and E represents grand challenges for synthetic chemists and will bring new horizons for the chemistry. There have been reports of M=E/M≡E multiple bonds for the majority of the transition metals, and even some actinide metals. In stark contrast, as the largest subgroup in the periodic table, rare-earth metals (Ln) were scarcely involved in Ln=E/Ln≡E multiple bonds. Until recently, there were a few examples of rare-earth monometallic alkylidene, imido and oxo complexes, featuring Ln=C/N/O bonds. What are in absence are rare-earth monometallic phosphinidene complexes with Ln=P bonds. Herein, we report synthesis and structure of rare-earth monometallic phosphinidene complexes, namely scandium phosphinophosphinidene complexes. Reactivity of scandium phosphinophosphinidene complexes is also mapped out, and appears to be easily tuned by the supporting ligand.

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Substitution reaction of triphenylphosphine oxide with rare-earth metal phosphido methyl complexes

Abstract: Rare-earth metal phosphido methyl complexes [LLn(Me){P(H)Ar}] react with triphenylphosphine oxide to give [LLn(Ph){CH2P(O)Ph2}], indicating C(alkyl)–P bond formation and C(aryl)–P bond cleavage.

Cited by 13 publications

References 16 publications

Scandium-Terminal Boronylphosphinidene Complex

Scandium-Terminal Boronylphosphinidene Complex

Monomeric Rare‐Earth Metal Silyl‐Thiophosphinoyl‐Alkylidene Complexes: Synthesis, Structure, and Reactivity

Synthesis and versatile reactivity of scandium phosphinophosphinidene complexes

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