Reactivity and isomerization of tert-butyldiallylphosphine with Os3 metallic cluster: Insights into the reaction mechanism and plausible intermediates through spectroscopic evidence and computational calculations

Deivi A. Oliveros R; María C. Goite; Alexander Briceño; Teresa González; Edgar Ocando-Mavárez; José R. Mora; Rubén A. Machado

doi:10.1016/j.jorganchem.2024.123048

Reactivity and isomerization of tert-butyldiallylphosphine with Os3 metallic cluster: Insights into the reaction mechanism and plausible intermediates through spectroscopic evidence and computational calculations

Deivi A. Oliveros R
, María C. Goite
, Alexander Briceño
, Teresa González
, Edgar Ocando-Mavárez
, José R. Mora
, Rubén A. Machado^*

^*Corresponding author for this work

Universidad Central de Venezuela, Facultad de Ciencias
Instituto Venezolano de Investigaciones Científicas (I.V.I.C.)

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

Abstract

The reaction of tert‑butyldiallylphosphine with [Os₃(CO)₁₀(CH₃CN)₂] give the compounds [Os₃(CO)₁₁{κ(P)-^tBuP(CH₂CH[dbnd]CH₂)₂}] 1a, [Os₃(CO)₁₁{κ(P)-^tBuP(CH[dbnd]CHCH₃)₂}] 1b, [Os₃(CO)₁₀{κ(P)-^tBuP(CH₂CH[dbnd]CH₂)₂}₂] 2, diastereoisomers [Os₃(CO)₁₀{µ:η²-κ³(P,C²,C³)-^tBuP(CH₂CH[dbnd]CH₂)₂}] (3a Sp, 3b Rp) and [Os₃(CO)₉{µ:η²-κ³(P,C²,C³)-^tBuP(CH₂CH[dbnd]CH₂)₂)(κ(P)-^tBuP(CH₂CH[dbnd]CH₂)₂}] (4a Sp, 4b Rp). Thermolysis of 2 or 3 gave the complexes [Os₃(CO)₈(μ-H){μ₃:η¹:η²:η²-κ⁵(P,C²,C³,C⁵,C⁶)-P(CH₂CH[dbnd]CH₂)(CH₂C[dbnd]CH₂)}] 5 and diastereoisomers [Os₃(CO)₈(µ-H)₂{µ₃:η¹:η¹:η²-κ³(P,C²,C³)-^tBuP(CH₂CH[dbnd]CH₂)(C[dbnd]CHCH₂)}] (6a Sp, 6b Rp). 1a, 1b, 3a, 5 and 6a which were characterized by X-ray analysis. To the best of our knowledge, 1b is the first characterized structure involving isomerization of the double bond of the allylic substituent at room temperature in the case of metallic clusters. X-ray coordinates were used to study the possible reaction mechanisms through computational calculations at the MN15L/def2svp level of theory, obtaining good agreement between experimental and computational results.

Original language	English
Article number	123048
Journal	Journal of Organometallic Chemistry
Volume	1008
DOIs	https://doi.org/10.1016/j.jorganchem.2024.123048
State	Published - 15 Mar 2024

Keywords

Allylphosphines
DFT calculations
Diastereoisomers
Isomerization
Trimetallic clusters

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10.1016/j.jorganchem.2024.123048

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Oliveros R, D. A., Goite, M. C., Briceño, A., González, T., Ocando-Mavárez, E., Mora, J. R., & Machado, R. A. (2024). Reactivity and isomerization of tert-butyldiallylphosphine with Os3 metallic cluster: Insights into the reaction mechanism and plausible intermediates through spectroscopic evidence and computational calculations. Journal of Organometallic Chemistry, 1008, Article 123048. https://doi.org/10.1016/j.jorganchem.2024.123048

@article{d2fa4da142b74b3b980aa7c6ed7fbf99,

title = "Reactivity and isomerization of tert-butyldiallylphosphine with Os3 metallic cluster: Insights into the reaction mechanism and plausible intermediates through spectroscopic evidence and computational calculations",

abstract = "The reaction of tert‑butyldiallylphosphine with [Os3(CO)10(CH3CN)2] give the compounds [Os3(CO)11\{κ(P)-tBuP(CH2CH[dbnd]CH2)2\}] 1a, [Os3(CO)11\{κ(P)-tBuP(CH[dbnd]CHCH3)2\}] 1b, [Os3(CO)10\{κ(P)-tBuP(CH2CH[dbnd]CH2)2\}2] 2, diastereoisomers [Os3(CO)10\{µ:η2-κ3(P,C2,C3)-tBuP(CH2CH[dbnd]CH2)2\}] (3a Sp, 3b Rp) and [Os3(CO)9\{µ:η2-κ3(P,C2,C3)-tBuP(CH2CH[dbnd]CH2)2)(κ(P)-tBuP(CH2CH[dbnd]CH2)2\}] (4a Sp, 4b Rp). Thermolysis of 2 or 3 gave the complexes [Os3(CO)8(μ-H)\{μ3:η1:η2:η2-κ5(P,C2,C3,C5,C6)-P(CH2CH[dbnd]CH2)(CH2C[dbnd]CH2)\}] 5 and diastereoisomers [Os3(CO)8(µ-H)2\{µ3:η1:η1:η2-κ3(P,C2,C3)-tBuP(CH2CH[dbnd]CH2)(C[dbnd]CHCH2)\}] (6a Sp, 6b Rp). 1a, 1b, 3a, 5 and 6a which were characterized by X-ray analysis. To the best of our knowledge, 1b is the first characterized structure involving isomerization of the double bond of the allylic substituent at room temperature in the case of metallic clusters. X-ray coordinates were used to study the possible reaction mechanisms through computational calculations at the MN15L/def2svp level of theory, obtaining good agreement between experimental and computational results.",

keywords = "Allylphosphines, DFT calculations, Diastereoisomers, Isomerization, Trimetallic clusters",

author = "\{Oliveros R\}, \{Deivi A.\} and Goite, \{Mar{\'i}a C.\} and Alexander Brice{\~n}o and Teresa Gonz{\'a}lez and Edgar Ocando-Mav{\'a}rez and Mora, \{Jos{\'e} R.\} and Machado, \{Rub{\'e}n A.\}",

note = "Publisher Copyright: {\textcopyright} 2024",

year = "2024",

month = mar,

day = "15",

doi = "10.1016/j.jorganchem.2024.123048",

language = "Ingl{\'e}s",

volume = "1008",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

publisher = "Elsevier B.V.",

}

Oliveros R, DA, Goite, MC, Briceño, A, González, T, Ocando-Mavárez, E, Mora, JR & Machado, RA 2024, 'Reactivity and isomerization of tert-butyldiallylphosphine with Os3 metallic cluster: Insights into the reaction mechanism and plausible intermediates through spectroscopic evidence and computational calculations', Journal of Organometallic Chemistry, vol. 1008, 123048. https://doi.org/10.1016/j.jorganchem.2024.123048

Reactivity and isomerization of tert-butyldiallylphosphine with Os3 metallic cluster: Insights into the reaction mechanism and plausible intermediates through spectroscopic evidence and computational calculations. / Oliveros R, Deivi A.; Goite, María C.; Briceño, Alexander et al.
In: Journal of Organometallic Chemistry, Vol. 1008, 123048, 15.03.2024.

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

TY - JOUR

T1 - Reactivity and isomerization of tert-butyldiallylphosphine with Os3 metallic cluster

T2 - Insights into the reaction mechanism and plausible intermediates through spectroscopic evidence and computational calculations

AU - Oliveros R, Deivi A.

AU - Goite, María C.

AU - Briceño, Alexander

AU - González, Teresa

AU - Ocando-Mavárez, Edgar

AU - Mora, José R.

AU - Machado, Rubén A.

PY - 2024/3/15

Y1 - 2024/3/15

N2 - The reaction of tert‑butyldiallylphosphine with [Os3(CO)10(CH3CN)2] give the compounds [Os3(CO)11{κ(P)-tBuP(CH2CH[dbnd]CH2)2}] 1a, [Os3(CO)11{κ(P)-tBuP(CH[dbnd]CHCH3)2}] 1b, [Os3(CO)10{κ(P)-tBuP(CH2CH[dbnd]CH2)2}2] 2, diastereoisomers [Os3(CO)10{µ:η2-κ3(P,C2,C3)-tBuP(CH2CH[dbnd]CH2)2}] (3a Sp, 3b Rp) and [Os3(CO)9{µ:η2-κ3(P,C2,C3)-tBuP(CH2CH[dbnd]CH2)2)(κ(P)-tBuP(CH2CH[dbnd]CH2)2}] (4a Sp, 4b Rp). Thermolysis of 2 or 3 gave the complexes [Os3(CO)8(μ-H){μ3:η1:η2:η2-κ5(P,C2,C3,C5,C6)-P(CH2CH[dbnd]CH2)(CH2C[dbnd]CH2)}] 5 and diastereoisomers [Os3(CO)8(µ-H)2{µ3:η1:η1:η2-κ3(P,C2,C3)-tBuP(CH2CH[dbnd]CH2)(C[dbnd]CHCH2)}] (6a Sp, 6b Rp). 1a, 1b, 3a, 5 and 6a which were characterized by X-ray analysis. To the best of our knowledge, 1b is the first characterized structure involving isomerization of the double bond of the allylic substituent at room temperature in the case of metallic clusters. X-ray coordinates were used to study the possible reaction mechanisms through computational calculations at the MN15L/def2svp level of theory, obtaining good agreement between experimental and computational results.

AB - The reaction of tert‑butyldiallylphosphine with [Os3(CO)10(CH3CN)2] give the compounds [Os3(CO)11{κ(P)-tBuP(CH2CH[dbnd]CH2)2}] 1a, [Os3(CO)11{κ(P)-tBuP(CH[dbnd]CHCH3)2}] 1b, [Os3(CO)10{κ(P)-tBuP(CH2CH[dbnd]CH2)2}2] 2, diastereoisomers [Os3(CO)10{µ:η2-κ3(P,C2,C3)-tBuP(CH2CH[dbnd]CH2)2}] (3a Sp, 3b Rp) and [Os3(CO)9{µ:η2-κ3(P,C2,C3)-tBuP(CH2CH[dbnd]CH2)2)(κ(P)-tBuP(CH2CH[dbnd]CH2)2}] (4a Sp, 4b Rp). Thermolysis of 2 or 3 gave the complexes [Os3(CO)8(μ-H){μ3:η1:η2:η2-κ5(P,C2,C3,C5,C6)-P(CH2CH[dbnd]CH2)(CH2C[dbnd]CH2)}] 5 and diastereoisomers [Os3(CO)8(µ-H)2{µ3:η1:η1:η2-κ3(P,C2,C3)-tBuP(CH2CH[dbnd]CH2)(C[dbnd]CHCH2)}] (6a Sp, 6b Rp). 1a, 1b, 3a, 5 and 6a which were characterized by X-ray analysis. To the best of our knowledge, 1b is the first characterized structure involving isomerization of the double bond of the allylic substituent at room temperature in the case of metallic clusters. X-ray coordinates were used to study the possible reaction mechanisms through computational calculations at the MN15L/def2svp level of theory, obtaining good agreement between experimental and computational results.

KW - Allylphosphines

KW - DFT calculations

KW - Diastereoisomers

KW - Isomerization

KW - Trimetallic clusters

UR - https://www.scopus.com/pages/publications/85185537097

U2 - 10.1016/j.jorganchem.2024.123048

DO - 10.1016/j.jorganchem.2024.123048

M3 - Artículo

AN - SCOPUS:85185537097

SN - 0022-328X

VL - 1008

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

M1 - 123048

ER -

Oliveros R DA, Goite MC, Briceño A, González T, Ocando-Mavárez E, Mora JR et al. Reactivity and isomerization of tert-butyldiallylphosphine with Os3 metallic cluster: Insights into the reaction mechanism and plausible intermediates through spectroscopic evidence and computational calculations. Journal of Organometallic Chemistry. 2024 Mar 15;1008:123048. doi: 10.1016/j.jorganchem.2024.123048

Reactivity and isomerization of tert-butyldiallylphosphine with Os3 metallic cluster: Insights into the reaction mechanism and plausible intermediates through spectroscopic evidence and computational calculations

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Keywords

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