Four-coordinate phosphinidene complexes of titanium prepared by α-H-migration: Phospha-staudinger and phosphaalkene-insertion reactions

Falguni Basuli; John Tomaszewski; John C. Huffman; Daniel J. Mindiola

doi:10.1021/ja036559r

Four-coordinate phosphinidene complexes of titanium prepared by α-H-migration: Phospha-staudinger and phosphaalkene-insertion reactions

Falguni Basuli
, John Tomaszewski
, John C. Huffman
, Daniel J. Mindiola

Department of Pathology and Anatomical Sciences

Indiana University Bloomington

Research output: Contribution to journal › Article › peer-review

109 Scopus citations

Abstract

α-Hydrogen migration in the phosphide (Nacnac)Ti=CH^tBu(PHR) (Nacnac- = [Ar]NC(Me)CHC(Me)N[Ar], Ar = 2,6^-iPr₂C₆H₃, R = C₆H₁₁, 2,4,6^-iPr₃C₆H₂, 2,4,6^-tBuC₆H₂), prepared from salt metathesis of (Nacnac)Ti=CH^tBu(PHR) with LiPHR, generatesterminal and four-coordinate phosphinidene complexes (Nacnac)Ti=PR(CH₂^tBu), one of which was structurally characterized (R = 2,4,6-^tBu₃C₆H₂). Phosphinidene intermediate (Nacnac)Ti=PR(CH₂^tBu) (R = C₆H₁₁, 2,4,6^-iPr₃C₆H₂) transform to ([Ar]NC(Me)CHC(Me)P[R][CH₂^tBu])Ti=NAr(OEt₂) through "phospha-Staudinger" and subsequent phosphaalkene-insertion reactions.

Original language	English
Pages (from-to)	10170-10171
Number of pages	2
Journal	Journal of the American Chemical Society
Volume	125
Issue number	34
DOIs	https://doi.org/10.1021/ja036559r
State	Published - Aug 27 2003

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@article{2fed8b41910b4078be2d6298da7e8562,

title = "Four-coordinate phosphinidene complexes of titanium prepared by α-H-migration: Phospha-staudinger and phosphaalkene-insertion reactions",

abstract = "α-Hydrogen migration in the phosphide (Nacnac)Ti=CHtBu(PHR) (Nacnac- = [Ar]NC(Me)CHC(Me)N[Ar], Ar = 2,6-iPr2C6H3, R = C6H11, 2,4,6-iPr3C6H2, 2,4,6-tBuC6H2), prepared from salt metathesis of (Nacnac)Ti=CHtBu(PHR) with LiPHR, generatesterminal and four-coordinate phosphinidene complexes (Nacnac)Ti=PR(CH2tBu), one of which was structurally characterized (R = 2,4,6-tBu3C6H2). Phosphinidene intermediate (Nacnac)Ti=PR(CH2tBu) (R = C6H11, 2,4,6-iPr3C6H2) transform to ([Ar]NC(Me)CHC(Me)P[R][CH2tBu])Ti=NAr(OEt2) through {"}phospha-Staudinger{"} and subsequent phosphaalkene-insertion reactions.",

author = "Falguni Basuli and John Tomaszewski and Huffman, \{John C.\} and Mindiola, \{Daniel J.\}",

year = "2003",

month = aug,

day = "27",

doi = "10.1021/ja036559r",

language = "English",

volume = "125",

pages = "10170--10171",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "34",

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TY - JOUR

T1 - Four-coordinate phosphinidene complexes of titanium prepared by α-H-migration

T2 - Phospha-staudinger and phosphaalkene-insertion reactions

AU - Basuli, Falguni

AU - Tomaszewski, John

AU - Huffman, John C.

AU - Mindiola, Daniel J.

PY - 2003/8/27

Y1 - 2003/8/27

N2 - α-Hydrogen migration in the phosphide (Nacnac)Ti=CHtBu(PHR) (Nacnac- = [Ar]NC(Me)CHC(Me)N[Ar], Ar = 2,6-iPr2C6H3, R = C6H11, 2,4,6-iPr3C6H2, 2,4,6-tBuC6H2), prepared from salt metathesis of (Nacnac)Ti=CHtBu(PHR) with LiPHR, generatesterminal and four-coordinate phosphinidene complexes (Nacnac)Ti=PR(CH2tBu), one of which was structurally characterized (R = 2,4,6-tBu3C6H2). Phosphinidene intermediate (Nacnac)Ti=PR(CH2tBu) (R = C6H11, 2,4,6-iPr3C6H2) transform to ([Ar]NC(Me)CHC(Me)P[R][CH2tBu])Ti=NAr(OEt2) through "phospha-Staudinger" and subsequent phosphaalkene-insertion reactions.

AB - α-Hydrogen migration in the phosphide (Nacnac)Ti=CHtBu(PHR) (Nacnac- = [Ar]NC(Me)CHC(Me)N[Ar], Ar = 2,6-iPr2C6H3, R = C6H11, 2,4,6-iPr3C6H2, 2,4,6-tBuC6H2), prepared from salt metathesis of (Nacnac)Ti=CHtBu(PHR) with LiPHR, generatesterminal and four-coordinate phosphinidene complexes (Nacnac)Ti=PR(CH2tBu), one of which was structurally characterized (R = 2,4,6-tBu3C6H2). Phosphinidene intermediate (Nacnac)Ti=PR(CH2tBu) (R = C6H11, 2,4,6-iPr3C6H2) transform to ([Ar]NC(Me)CHC(Me)P[R][CH2tBu])Ti=NAr(OEt2) through "phospha-Staudinger" and subsequent phosphaalkene-insertion reactions.

UR - https://www.scopus.com/pages/publications/0041931083

U2 - 10.1021/ja036559r

DO - 10.1021/ja036559r

M3 - Article

AN - SCOPUS:0041931083

SN - 0002-7863

VL - 125

SP - 10170

EP - 10171

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 34

ER -

Four-coordinate phosphinidene complexes of titanium prepared by α-H-migration: Phospha-staudinger and phosphaalkene-insertion reactions

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