Chemistry of [(1H-hydronaphthalene)Mn(CO)3]: The role of ring-slippage in substitution, catalytic hydrosilylation, and molecular crystal structure of [(η3-C10H9)Mn(CO)3P(OMe) 3]

Seung Uk Son; Se Jung Paik; In Su Lee; Young A. Lee; Young Keun Chung; Won K. Seok; Heung N. Lee

doi:10.1021/om9903386

Chemistry of [(1H-hydronaphthalene)Mn(CO)₃]: The role of ring-slippage in substitution, catalytic hydrosilylation, and molecular crystal structure of [(η³-C₁₀H₉)Mn(CO)₃P(OMe) ₃]

Seung Uk Son
, Se Jung Paik
, In Su Lee
, Young A. Lee
, Young Keun Chung^*
, Won K. Seok
, Heung N. Lee

^*Corresponding author for this work

Department of Chemistry

Seoul National University
Dongguk University

Research output: Contribution to journal › Journal article › peer-review

52 Scopus citations

Abstract

Reaction of [(η⁵-C₁₀H₉)Mn(CO)₃] (1) with L produced [(η³-C₁₀H₉)Mn(CO)₃L] (2, L = P(OMe)₃; 5, L = CO) in high yields. X-ray structural analysis of 2 confirmed an η³-bonding mode of the 1-hydronaphthalene ring. Thermal treatment of 2 led to [(η⁵-C₁₀H₉)Mn(CO)₂P(OMe) ₃] (3). The η⁵-1-hydronaphthalene ring in 1 is quite easily ring-slipped, η⁵ ↔ η³. A kinetic study of the reaction of 1 with P(OMe)₃ indicates that formation of 2 is first order in 1 and first order in P(OMe)₃ with the following activation parameters: ΔH^‡ = 6.9 ± 0.4 kcal/mol; ΔS^‡ = -32.6 ± 1.5 eu. Quantitative comparison between the reactivity of the indenyl complex [(η⁵-C₉H₇)Mn(CO)₃] with P(OEt)₃ and 1 with P(OMe)₃ at 130°C shows that the rate constant for 1 is 2 × 10⁶ times faster than that of the indenyl complex. The tremendous rate enhancement in 1 was rationalized as a stabilization of 2 by the second benzene ring. The facile ring-slippage in 1 has been utilized in the synthesis of [(η⁶-C₁₀H₈)Mn(CO)₂P(OMe) ₃]-BF₄ and in the catalytic hydrosilylation of ketones. Complex 1 is an effective catalyst for the hydrosilylation of alkyl and aryl ketones with Ph₂SiH₂ as a silane source. The indenyl complex [(η⁵-C₉H₇)Mn(CO)₃] has no catalytic activity in the hydrosilylation of ketones. The facile ring-slippage in the η⁵-1-hydronaphthalene ring plays a crucial role in the chemistry of 1.

Original language	English
Pages (from-to)	4114-4118
Number of pages	5
Journal	Organometallics
Volume	18
Issue number	20
DOIs	https://doi.org/10.1021/om9903386
State	Published - 1999.09.27

Access to Document

10.1021/om9903386

Cite this

@article{c010c04a329248a2a296c9dda58607e1,

title = "Chemistry of [(1H-hydronaphthalene)Mn(CO)3]: The role of ring-slippage in substitution, catalytic hydrosilylation, and molecular crystal structure of [(η3-C10H9)Mn(CO)3P(OMe) 3]",

abstract = "Reaction of [(η5-C10H9)Mn(CO)3] (1) with L produced [(η3-C10H9)Mn(CO)3L] (2, L = P(OMe)3; 5, L = CO) in high yields. X-ray structural analysis of 2 confirmed an η3-bonding mode of the 1-hydronaphthalene ring. Thermal treatment of 2 led to [(η5-C10H9)Mn(CO)2P(OMe) 3] (3). The η5-1-hydronaphthalene ring in 1 is quite easily ring-slipped, η5 ↔ η3. A kinetic study of the reaction of 1 with P(OMe)3 indicates that formation of 2 is first order in 1 and first order in P(OMe)3 with the following activation parameters: ΔH‡ = 6.9 ± 0.4 kcal/mol; ΔS‡ = -32.6 ± 1.5 eu. Quantitative comparison between the reactivity of the indenyl complex [(η5-C9H7)Mn(CO)3] with P(OEt)3 and 1 with P(OMe)3 at 130°C shows that the rate constant for 1 is 2 × 106 times faster than that of the indenyl complex. The tremendous rate enhancement in 1 was rationalized as a stabilization of 2 by the second benzene ring. The facile ring-slippage in 1 has been utilized in the synthesis of [(η6-C10H8)Mn(CO)2P(OMe) 3]-BF4 and in the catalytic hydrosilylation of ketones. Complex 1 is an effective catalyst for the hydrosilylation of alkyl and aryl ketones with Ph2SiH2 as a silane source. The indenyl complex [(η5-C9H7)Mn(CO)3] has no catalytic activity in the hydrosilylation of ketones. The facile ring-slippage in the η5-1-hydronaphthalene ring plays a crucial role in the chemistry of 1.",

author = "Son, \{Seung Uk\} and Paik, \{Se Jung\} and Lee, \{In Su\} and Lee, \{Young A.\} and Chung, \{Young Keun\} and Seok, \{Won K.\} and Lee, \{Heung N.\}",

year = "1999",

month = sep,

day = "27",

doi = "10.1021/om9903386",

language = "English",

volume = "18",

pages = "4114--4118",

journal = "Organometallics",

issn = "0276-7333",

number = "20",

}

TY - JOUR

T1 - Chemistry of [(1H-hydronaphthalene)Mn(CO)3]

T2 - The role of ring-slippage in substitution, catalytic hydrosilylation, and molecular crystal structure of [(η3-C10H9)Mn(CO)3P(OMe) 3]

AU - Son, Seung Uk

AU - Paik, Se Jung

AU - Lee, In Su

AU - Lee, Young A.

AU - Chung, Young Keun

AU - Seok, Won K.

AU - Lee, Heung N.

PY - 1999/9/27

Y1 - 1999/9/27

N2 - Reaction of [(η5-C10H9)Mn(CO)3] (1) with L produced [(η3-C10H9)Mn(CO)3L] (2, L = P(OMe)3; 5, L = CO) in high yields. X-ray structural analysis of 2 confirmed an η3-bonding mode of the 1-hydronaphthalene ring. Thermal treatment of 2 led to [(η5-C10H9)Mn(CO)2P(OMe) 3] (3). The η5-1-hydronaphthalene ring in 1 is quite easily ring-slipped, η5 ↔ η3. A kinetic study of the reaction of 1 with P(OMe)3 indicates that formation of 2 is first order in 1 and first order in P(OMe)3 with the following activation parameters: ΔH‡ = 6.9 ± 0.4 kcal/mol; ΔS‡ = -32.6 ± 1.5 eu. Quantitative comparison between the reactivity of the indenyl complex [(η5-C9H7)Mn(CO)3] with P(OEt)3 and 1 with P(OMe)3 at 130°C shows that the rate constant for 1 is 2 × 106 times faster than that of the indenyl complex. The tremendous rate enhancement in 1 was rationalized as a stabilization of 2 by the second benzene ring. The facile ring-slippage in 1 has been utilized in the synthesis of [(η6-C10H8)Mn(CO)2P(OMe) 3]-BF4 and in the catalytic hydrosilylation of ketones. Complex 1 is an effective catalyst for the hydrosilylation of alkyl and aryl ketones with Ph2SiH2 as a silane source. The indenyl complex [(η5-C9H7)Mn(CO)3] has no catalytic activity in the hydrosilylation of ketones. The facile ring-slippage in the η5-1-hydronaphthalene ring plays a crucial role in the chemistry of 1.

AB - Reaction of [(η5-C10H9)Mn(CO)3] (1) with L produced [(η3-C10H9)Mn(CO)3L] (2, L = P(OMe)3; 5, L = CO) in high yields. X-ray structural analysis of 2 confirmed an η3-bonding mode of the 1-hydronaphthalene ring. Thermal treatment of 2 led to [(η5-C10H9)Mn(CO)2P(OMe) 3] (3). The η5-1-hydronaphthalene ring in 1 is quite easily ring-slipped, η5 ↔ η3. A kinetic study of the reaction of 1 with P(OMe)3 indicates that formation of 2 is first order in 1 and first order in P(OMe)3 with the following activation parameters: ΔH‡ = 6.9 ± 0.4 kcal/mol; ΔS‡ = -32.6 ± 1.5 eu. Quantitative comparison between the reactivity of the indenyl complex [(η5-C9H7)Mn(CO)3] with P(OEt)3 and 1 with P(OMe)3 at 130°C shows that the rate constant for 1 is 2 × 106 times faster than that of the indenyl complex. The tremendous rate enhancement in 1 was rationalized as a stabilization of 2 by the second benzene ring. The facile ring-slippage in 1 has been utilized in the synthesis of [(η6-C10H8)Mn(CO)2P(OMe) 3]-BF4 and in the catalytic hydrosilylation of ketones. Complex 1 is an effective catalyst for the hydrosilylation of alkyl and aryl ketones with Ph2SiH2 as a silane source. The indenyl complex [(η5-C9H7)Mn(CO)3] has no catalytic activity in the hydrosilylation of ketones. The facile ring-slippage in the η5-1-hydronaphthalene ring plays a crucial role in the chemistry of 1.

UR - https://www.scopus.com/pages/publications/0001331707

U2 - 10.1021/om9903386

DO - 10.1021/om9903386

M3 - Journal article

AN - SCOPUS:0001331707

SN - 0276-7333

VL - 18

SP - 4114

EP - 4118

JO - Organometallics

JF - Organometallics

IS - 20

ER -

Chemistry of [(1H-hydronaphthalene)Mn(CO)₃]: The role of ring-slippage in substitution, catalytic hydrosilylation, and molecular crystal structure of [(η³-C₁₀H₉)Mn(CO)₃P(OMe) ₃]

Abstract

Access to Document

Other files and links

Fingerprint

Cite this