he reactions of dicarbonylbis(phosphorus donor) iron fragments with tertiary propargyl alcohols

Christine Gauss, Dario Veghini, Olli Orama, Heinz Berke (Corresponding Author)

Research output: Contribution to journalArticleScientificpeer-review

26 Citations (Scopus)

Abstract

The reaction of the mixture of Fe(CO)2(PEt3)2N2 (1a) and [Fe(CO)2(PEt3)2]2N2 (1b) with propargyl alcohols HC≡C-CR1R2OH (R1 = R2 = Me; R1 = Me, R2 = Et; R1 = Me, R2 = iPr; R1 = Me; R2 = tBu; R1 = R2 = tBu; R1 = R2 = Ph) in THF affords isolable Fe(CO)2(PEt3)2(H)(C≡C-CR1R2OH) complexes (R1 = R2 = Me 2a; R1 = Me, R2 = Et 2b; R1 = Me, R2 = iPr 2c; R1 = Me, R2 = tBu 2d; R1 = R2 = tBu 2e; R1 = R2 = Ph 2f). Complexes 2a-d underwent dehydration in hexane in the presence of silylated silica to yield vinylvinylidene complexes Fe(CO)2(PEt3)2 =C=C(H)R′C-CR″R‴ (R′ = Me, R″, R‴ = H 3a; R′ = R″ = Me, R‴ = H 3b; R′ = R‴ = Me, R″ = H 3c; R′ = R″ = R‴ = Me 3d; R′ = tBu, R″ = R‴ = H 3e). 2e and 2f did not eliminate water. However, double deprotonation with n-BuLi and deoxygenation with acetyl chloride ultimately produced then their formal products of dehydration: di(t-butyl) or diphenylallenylidene(dicarbonyl)bis(triethylphosphine)iron compounds 4a or 4b. The reactions of dicarbonylbis(trimethylphosphite)iodoferrate 1b with the same propargyl alcohol derivatives HC≡C-CR1R2OH as mentioned above resulted in the formation of dicarbonylbistrimethylphosphite(vinylidene)iron derivatives Fe(CO)2[P(OMe)3]2 =C=C(H)CR1R2OH (R1 = R2 = Me) 7a; R1 = Me; R2 = Et 7b; R1 = Me, R2 = iPr; 7c; R1 = Me, R2 = tBu 7d; R1 = R2 = tBu 7e; R1 = R2 = Ph 7f). Dehydration processes of 7a–f in the presence of Al2O3 or SiO2 led to allenylidene or vinylvinylidene complexes Fe(CO)2[P(OMe)3]2 =C=C=CR1R2 (R1 = Me, R2 = tBu 8a; R1R2 = tBu 8b; R1 = R2 = Ph 8c) or Fe(CO)2[P(OMe)3]2 =C=C(H)CR′ =CR″R‴ (R′ = Me, R″ = R‴ = H 9a; R′ = Et, R″ = R‴ = H 9b; R′ = R″ = Me, R‴ = H 9c; R′ = R‴ = Me, R″ = H 9d; R′ = iPr, R″ = R‴ = H 9e; R′ = R″ = R‴ = Me 9f; R′ = tBu, R″ = R‴ = H 9g). 8c was also prepared by an alternative route starting from 1c and HC≡C-CPh2OAc which provided a higher yield. 7e and 8b were characterized by single crystal X-ray diffraction studies.

Original languageEnglish
Pages (from-to)19 - 38
Number of pages20
JournalJournal of Organometallic Chemistry
Volume541
Issue number1-2
DOIs
Publication statusPublished - 1997
MoE publication typeA1 Journal article-refereed

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Carbon Monoxide
Dehydration
Phosphorus
phosphorus
alcohols
Alcohols
Iron
fragments
dehydration
iron
Iron compounds
Derivatives
Deprotonation
deoxygenation
Hexane
iron compounds
vinylidene
Silica
Single crystals
X ray diffraction

Cite this

Gauss, Christine ; Veghini, Dario ; Orama, Olli ; Berke, Heinz. / he reactions of dicarbonylbis(phosphorus donor) iron fragments with tertiary propargyl alcohols. In: Journal of Organometallic Chemistry. 1997 ; Vol. 541, No. 1-2. pp. 19 - 38.
@article{153f49561f074e908295e4681a453324,
title = "he reactions of dicarbonylbis(phosphorus donor) iron fragments with tertiary propargyl alcohols",
abstract = "The reaction of the mixture of Fe(CO)2(PEt3)2N2 (1a) and [Fe(CO)2(PEt3)2]2N2 (1b) with propargyl alcohols HC≡C-CR1R2OH (R1 = R2 = Me; R1 = Me, R2 = Et; R1 = Me, R2 = iPr; R1 = Me; R2 = tBu; R1 = R2 = tBu; R1 = R2 = Ph) in THF affords isolable Fe(CO)2(PEt3)2(H)(C≡C-CR1R2OH) complexes (R1 = R2 = Me 2a; R1 = Me, R2 = Et 2b; R1 = Me, R2 = iPr 2c; R1 = Me, R2 = tBu 2d; R1 = R2 = tBu 2e; R1 = R2 = Ph 2f). Complexes 2a-d underwent dehydration in hexane in the presence of silylated silica to yield vinylvinylidene complexes Fe(CO)2(PEt3)2 =C=C(H)R′C-CR″R‴ (R′ = Me, R″, R‴ = H 3a; R′ = R″ = Me, R‴ = H 3b; R′ = R‴ = Me, R″ = H 3c; R′ = R″ = R‴ = Me 3d; R′ = tBu, R″ = R‴ = H 3e). 2e and 2f did not eliminate water. However, double deprotonation with n-BuLi and deoxygenation with acetyl chloride ultimately produced then their formal products of dehydration: di(t-butyl) or diphenylallenylidene(dicarbonyl)bis(triethylphosphine)iron compounds 4a or 4b. The reactions of dicarbonylbis(trimethylphosphite)iodoferrate 1b with the same propargyl alcohol derivatives HC≡C-CR1R2OH as mentioned above resulted in the formation of dicarbonylbistrimethylphosphite(vinylidene)iron derivatives Fe(CO)2[P(OMe)3]2 =C=C(H)CR1R2OH (R1 = R2 = Me) 7a; R1 = Me; R2 = Et 7b; R1 = Me, R2 = iPr; 7c; R1 = Me, R2 = tBu 7d; R1 = R2 = tBu 7e; R1 = R2 = Ph 7f). Dehydration processes of 7a–f in the presence of Al2O3 or SiO2 led to allenylidene or vinylvinylidene complexes Fe(CO)2[P(OMe)3]2 =C=C=CR1R2 (R1 = Me, R2 = tBu 8a; R1R2 = tBu 8b; R1 = R2 = Ph 8c) or Fe(CO)2[P(OMe)3]2 =C=C(H)CR′ =CR″R‴ (R′ = Me, R″ = R‴ = H 9a; R′ = Et, R″ = R‴ = H 9b; R′ = R″ = Me, R‴ = H 9c; R′ = R‴ = Me, R″ = H 9d; R′ = iPr, R″ = R‴ = H 9e; R′ = R″ = R‴ = Me 9f; R′ = tBu, R″ = R‴ = H 9g). 8c was also prepared by an alternative route starting from 1c and HC≡C-CPh2OAc which provided a higher yield. 7e and 8b were characterized by single crystal X-ray diffraction studies.",
author = "Christine Gauss and Dario Veghini and Olli Orama and Heinz Berke",
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year = "1997",
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language = "English",
volume = "541",
pages = "19 -- 38",
journal = "Journal of Organometallic Chemistry",
issn = "0022-328X",
publisher = "Elsevier",
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he reactions of dicarbonylbis(phosphorus donor) iron fragments with tertiary propargyl alcohols. / Gauss, Christine; Veghini, Dario; Orama, Olli; Berke, Heinz (Corresponding Author).

In: Journal of Organometallic Chemistry, Vol. 541, No. 1-2, 1997, p. 19 - 38.

Research output: Contribution to journalArticleScientificpeer-review

TY - JOUR

T1 - he reactions of dicarbonylbis(phosphorus donor) iron fragments with tertiary propargyl alcohols

AU - Gauss, Christine

AU - Veghini, Dario

AU - Orama, Olli

AU - Berke, Heinz

N1 - Project code: K7SU00052

PY - 1997

Y1 - 1997

N2 - The reaction of the mixture of Fe(CO)2(PEt3)2N2 (1a) and [Fe(CO)2(PEt3)2]2N2 (1b) with propargyl alcohols HC≡C-CR1R2OH (R1 = R2 = Me; R1 = Me, R2 = Et; R1 = Me, R2 = iPr; R1 = Me; R2 = tBu; R1 = R2 = tBu; R1 = R2 = Ph) in THF affords isolable Fe(CO)2(PEt3)2(H)(C≡C-CR1R2OH) complexes (R1 = R2 = Me 2a; R1 = Me, R2 = Et 2b; R1 = Me, R2 = iPr 2c; R1 = Me, R2 = tBu 2d; R1 = R2 = tBu 2e; R1 = R2 = Ph 2f). Complexes 2a-d underwent dehydration in hexane in the presence of silylated silica to yield vinylvinylidene complexes Fe(CO)2(PEt3)2 =C=C(H)R′C-CR″R‴ (R′ = Me, R″, R‴ = H 3a; R′ = R″ = Me, R‴ = H 3b; R′ = R‴ = Me, R″ = H 3c; R′ = R″ = R‴ = Me 3d; R′ = tBu, R″ = R‴ = H 3e). 2e and 2f did not eliminate water. However, double deprotonation with n-BuLi and deoxygenation with acetyl chloride ultimately produced then their formal products of dehydration: di(t-butyl) or diphenylallenylidene(dicarbonyl)bis(triethylphosphine)iron compounds 4a or 4b. The reactions of dicarbonylbis(trimethylphosphite)iodoferrate 1b with the same propargyl alcohol derivatives HC≡C-CR1R2OH as mentioned above resulted in the formation of dicarbonylbistrimethylphosphite(vinylidene)iron derivatives Fe(CO)2[P(OMe)3]2 =C=C(H)CR1R2OH (R1 = R2 = Me) 7a; R1 = Me; R2 = Et 7b; R1 = Me, R2 = iPr; 7c; R1 = Me, R2 = tBu 7d; R1 = R2 = tBu 7e; R1 = R2 = Ph 7f). Dehydration processes of 7a–f in the presence of Al2O3 or SiO2 led to allenylidene or vinylvinylidene complexes Fe(CO)2[P(OMe)3]2 =C=C=CR1R2 (R1 = Me, R2 = tBu 8a; R1R2 = tBu 8b; R1 = R2 = Ph 8c) or Fe(CO)2[P(OMe)3]2 =C=C(H)CR′ =CR″R‴ (R′ = Me, R″ = R‴ = H 9a; R′ = Et, R″ = R‴ = H 9b; R′ = R″ = Me, R‴ = H 9c; R′ = R‴ = Me, R″ = H 9d; R′ = iPr, R″ = R‴ = H 9e; R′ = R″ = R‴ = Me 9f; R′ = tBu, R″ = R‴ = H 9g). 8c was also prepared by an alternative route starting from 1c and HC≡C-CPh2OAc which provided a higher yield. 7e and 8b were characterized by single crystal X-ray diffraction studies.

AB - The reaction of the mixture of Fe(CO)2(PEt3)2N2 (1a) and [Fe(CO)2(PEt3)2]2N2 (1b) with propargyl alcohols HC≡C-CR1R2OH (R1 = R2 = Me; R1 = Me, R2 = Et; R1 = Me, R2 = iPr; R1 = Me; R2 = tBu; R1 = R2 = tBu; R1 = R2 = Ph) in THF affords isolable Fe(CO)2(PEt3)2(H)(C≡C-CR1R2OH) complexes (R1 = R2 = Me 2a; R1 = Me, R2 = Et 2b; R1 = Me, R2 = iPr 2c; R1 = Me, R2 = tBu 2d; R1 = R2 = tBu 2e; R1 = R2 = Ph 2f). Complexes 2a-d underwent dehydration in hexane in the presence of silylated silica to yield vinylvinylidene complexes Fe(CO)2(PEt3)2 =C=C(H)R′C-CR″R‴ (R′ = Me, R″, R‴ = H 3a; R′ = R″ = Me, R‴ = H 3b; R′ = R‴ = Me, R″ = H 3c; R′ = R″ = R‴ = Me 3d; R′ = tBu, R″ = R‴ = H 3e). 2e and 2f did not eliminate water. However, double deprotonation with n-BuLi and deoxygenation with acetyl chloride ultimately produced then their formal products of dehydration: di(t-butyl) or diphenylallenylidene(dicarbonyl)bis(triethylphosphine)iron compounds 4a or 4b. The reactions of dicarbonylbis(trimethylphosphite)iodoferrate 1b with the same propargyl alcohol derivatives HC≡C-CR1R2OH as mentioned above resulted in the formation of dicarbonylbistrimethylphosphite(vinylidene)iron derivatives Fe(CO)2[P(OMe)3]2 =C=C(H)CR1R2OH (R1 = R2 = Me) 7a; R1 = Me; R2 = Et 7b; R1 = Me, R2 = iPr; 7c; R1 = Me, R2 = tBu 7d; R1 = R2 = tBu 7e; R1 = R2 = Ph 7f). Dehydration processes of 7a–f in the presence of Al2O3 or SiO2 led to allenylidene or vinylvinylidene complexes Fe(CO)2[P(OMe)3]2 =C=C=CR1R2 (R1 = Me, R2 = tBu 8a; R1R2 = tBu 8b; R1 = R2 = Ph 8c) or Fe(CO)2[P(OMe)3]2 =C=C(H)CR′ =CR″R‴ (R′ = Me, R″ = R‴ = H 9a; R′ = Et, R″ = R‴ = H 9b; R′ = R″ = Me, R‴ = H 9c; R′ = R‴ = Me, R″ = H 9d; R′ = iPr, R″ = R‴ = H 9e; R′ = R″ = R‴ = Me 9f; R′ = tBu, R″ = R‴ = H 9g). 8c was also prepared by an alternative route starting from 1c and HC≡C-CPh2OAc which provided a higher yield. 7e and 8b were characterized by single crystal X-ray diffraction studies.

U2 - 10.1016/S0022-328X(97)00012-0

DO - 10.1016/S0022-328X(97)00012-0

M3 - Article

VL - 541

SP - 19

EP - 38

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

SN - 0022-328X

IS - 1-2

ER -