Synthesis, characterization, and reactivity of PPN[Cr(CO)4(NO)]

Daniel R. Mantell; Wayne L. Gladfelter

doi:10.1016/0022-328X(88)80157-8

Synthesis, characterization, and reactivity of PPN[Cr(CO)₄(NO)]

Daniel R. Mantell, Wayne L. Gladfelter

Chemistry (Twin Cities)

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

24 Scopus citations

Abstract

The new nitrosyl carbonylmetalate PPN[Cr(CO)₄(NO)] has been synthesized from Cr(CO)₆ and PPN(NO₂) in THF (PPN = bis(triphenylphosphine)iminium cation). The material was characterized by infrared and ¹⁵N NMR spectroscopy and by elemental analysis, which demonstrated it has the same structure as Mn(CO)₄(NO). Kinetic experiments show the reaction to be first order in both chromium and nitrite with k = 0.25 ± 0.05 M^-1 sec^-1 at 58.60 ± 0.05°C. A mechanism consistent with this and related results is discussed. Metalcarbon, metalhydrogen, and metalmetal bonds have been formed by the reactions of PPN[Cr(CO)₄(NO)] with eletrophiles (CF₃SO₃CH₃, CF₃SO₃H, Ph₃SnCl). With the labile complexes, M(CO)₅(THF) (M = Cr, Mo and W), PPN[Cr(CO)₄(NO)] produces the homo- and hetero-dinuclear complexes PPN[CrM(CO)₉(NO)] (M = Cr, Mo and W).

Original language	English (US)
Pages (from-to)	333-342
Number of pages	10
Journal	Journal of Organometallic Chemistry
Volume	347
Issue number	3
DOIs	https://doi.org/10.1016/0022-328X(88)80157-8
State	Published - Jun 21 1988

Bibliographical note

Funding Information:
This research was supported by a grant from the National Science Foundation.

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10.1016/0022-328X(88)80157-8

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@article{7309756a6b1c4d56902971c504fa803b,

title = "Synthesis, characterization, and reactivity of PPN[Cr(CO)4(NO)]",

abstract = "The new nitrosyl carbonylmetalate PPN[Cr(CO)4(NO)] has been synthesized from Cr(CO)6 and PPN(NO2) in THF (PPN = bis(triphenylphosphine)iminium cation). The material was characterized by infrared and 15N NMR spectroscopy and by elemental analysis, which demonstrated it has the same structure as Mn(CO)4(NO). Kinetic experiments show the reaction to be first order in both chromium and nitrite with k = 0.25 ± 0.05 M-1 sec-1 at 58.60 ± 0.05°C. A mechanism consistent with this and related results is discussed. Metalcarbon, metalhydrogen, and metalmetal bonds have been formed by the reactions of PPN[Cr(CO)4(NO)] with eletrophiles (CF3SO3CH3, CF3SO3H, Ph3SnCl). With the labile complexes, M(CO)5(THF) (M = Cr, Mo and W), PPN[Cr(CO)4(NO)] produces the homo- and hetero-dinuclear complexes PPN[CrM(CO)9(NO)] (M = Cr, Mo and W).",

author = "Mantell, {Daniel R.} and Gladfelter, {Wayne L.}",

note = "Funding Information: This research was supported by a grant from the National Science Foundation.",

year = "1988",

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doi = "10.1016/0022-328X(88)80157-8",

language = "English (US)",

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T1 - Synthesis, characterization, and reactivity of PPN[Cr(CO)4(NO)]

AU - Mantell, Daniel R.

AU - Gladfelter, Wayne L.

N1 - Funding Information: This research was supported by a grant from the National Science Foundation.

PY - 1988/6/21

Y1 - 1988/6/21

N2 - The new nitrosyl carbonylmetalate PPN[Cr(CO)4(NO)] has been synthesized from Cr(CO)6 and PPN(NO2) in THF (PPN = bis(triphenylphosphine)iminium cation). The material was characterized by infrared and 15N NMR spectroscopy and by elemental analysis, which demonstrated it has the same structure as Mn(CO)4(NO). Kinetic experiments show the reaction to be first order in both chromium and nitrite with k = 0.25 ± 0.05 M-1 sec-1 at 58.60 ± 0.05°C. A mechanism consistent with this and related results is discussed. Metalcarbon, metalhydrogen, and metalmetal bonds have been formed by the reactions of PPN[Cr(CO)4(NO)] with eletrophiles (CF3SO3CH3, CF3SO3H, Ph3SnCl). With the labile complexes, M(CO)5(THF) (M = Cr, Mo and W), PPN[Cr(CO)4(NO)] produces the homo- and hetero-dinuclear complexes PPN[CrM(CO)9(NO)] (M = Cr, Mo and W).

AB - The new nitrosyl carbonylmetalate PPN[Cr(CO)4(NO)] has been synthesized from Cr(CO)6 and PPN(NO2) in THF (PPN = bis(triphenylphosphine)iminium cation). The material was characterized by infrared and 15N NMR spectroscopy and by elemental analysis, which demonstrated it has the same structure as Mn(CO)4(NO). Kinetic experiments show the reaction to be first order in both chromium and nitrite with k = 0.25 ± 0.05 M-1 sec-1 at 58.60 ± 0.05°C. A mechanism consistent with this and related results is discussed. Metalcarbon, metalhydrogen, and metalmetal bonds have been formed by the reactions of PPN[Cr(CO)4(NO)] with eletrophiles (CF3SO3CH3, CF3SO3H, Ph3SnCl). With the labile complexes, M(CO)5(THF) (M = Cr, Mo and W), PPN[Cr(CO)4(NO)] produces the homo- and hetero-dinuclear complexes PPN[CrM(CO)9(NO)] (M = Cr, Mo and W).

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