Directed synthesis of the triangular mixed-metal cluster H 2RhRe2Cp*(CO)9: Ligand fluxionality and facile cluster fragmentation in the presence of CO, halogenated solvents, and thiols

Shih Huang Huang; William H. Watson; Carl J. Carrano; Xiaoping Wang; Michael G. Richmond

doi:10.1021/om9007407

Directed synthesis of the triangular mixed-metal cluster H ₂RhRe₂Cp*(CO)₉: Ligand fluxionality and facile cluster fragmentation in the presence of CO, halogenated solvents, and thiols

Shih Huang Huang, William H. Watson, Carl J. Carrano, Xiaoping Wang, Michael G. Richmond

Single Crystal Diffraction

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

12 Scopus citations

Abstract

The reaction Of H₂Re₂(CO)₈ (1) with Cp*Rh(CO)₂ (2) in refluxing hexane affords the mixed-metal clusters H₂RhRe₂Cp*(CO)₉ (4, major product), HRh₂ReCp*₂(CO)₆ (5), and HRhRe₃Cp*(CO)₁₄ (6). 4 and 5 are electron-precise 48e clusters and display triangular metallic cores, while 6 contains 64 valence electrons and exhibits a spiked-triangular core having a pendant Re(CO) ₅ moiety. Heating 1 with Cp*₂Rh₂(CO) ₂ (3) gives 4 and 5 as the principal products, in addition to H ₂Rh₂Re₂Cp*₂(CO)₈ (7) in low yield. Cluster 7 possesses 60e and contains a tetrametallic core with two face-capping CO and hydride groups. Heating 4 under CO leads to cluster fragmentation and formation of Re2(CO)io and 2 in essentially quantitative yield, as assessed by IR spectroscopy. The kinetics for the fragmentation of 4 in toluene under CO have been investigated over the temperature range 325-349 K by UV-vis spectroscopy. On the basis of the first-order rate constants and the Eyring activation parameters (ΔH‡ = 25.0(8) kcal/mol; ΔS‡ = -2.6(3) eu), a rate-limiting step involving a polyhedral opening of 4 is supported. 4 is thermally and photochemically sensitive, and reactions conducted in the presence of chlorinated solvents furnish the face-shared bioctahedral compound Cp*Rh(μ-Cl)₃Re(CO) ₃ (8). Heating 4 and H₂S in benzene at ca. 60 °C furnishes the 48e triangular cluster S₂Rh₃Cp*(CO) ₄ (9), which contains two Rh(CO)₂ moieties and two face-capping sulfide groups. The reaction of 4 with p-methylbenzenethiol gives the sulfido-bridged dimer Cp*Rh(μSC₆H₄Me-p) ₃Re(CO)₃ (11). The dinuclear compounds Cp*Rh(μ-Cl)(μ-SC₆H₄Me-p)₂Re(CO) ₃ (10) and 11 are formed when 8 is allowed to react with p-methylbenzenethiol. Treatment of 8 and 10 with excess p-methylbenzenethiol yields 11 at elevated temperature in toluene. Compounds 4-11 have been isolated and fully characterized by IR and NMR spectroscopy and by X-ray crystallography. The reactivity displayed by 4 is contrasted with that of the known indenyl-substituted cluster H₂Re₂Ir(η⁵-ind) (CO)₉ prepared earlier by Shapley and co-workers.

Original language	English
Pages (from-to)	61-75
Number of pages	15
Journal	Organometallics
Volume	29
Issue number	1
DOIs	https://doi.org/10.1021/om9007407
State	Published - Jan 11 2010

Access to Document

10.1021/om9007407

Cite this

@article{f0eaa45c37dd450fabf32361c2e14d2c,

title = "Directed synthesis of the triangular mixed-metal cluster H 2RhRe2Cp*(CO)9: Ligand fluxionality and facile cluster fragmentation in the presence of CO, halogenated solvents, and thiols",

abstract = "The reaction Of H2Re2(CO)8 (1) with Cp*Rh(CO)2 (2) in refluxing hexane affords the mixed-metal clusters H2RhRe2Cp*(CO)9 (4, major product), HRh2ReCp*2(CO)6 (5), and HRhRe3Cp*(CO)14 (6). 4 and 5 are electron-precise 48e clusters and display triangular metallic cores, while 6 contains 64 valence electrons and exhibits a spiked-triangular core having a pendant Re(CO) 5 moiety. Heating 1 with Cp*2Rh2(CO) 2 (3) gives 4 and 5 as the principal products, in addition to H 2Rh2Re2Cp*2(CO)8 (7) in low yield. Cluster 7 possesses 60e and contains a tetrametallic core with two face-capping CO and hydride groups. Heating 4 under CO leads to cluster fragmentation and formation of Re2(CO)io and 2 in essentially quantitative yield, as assessed by IR spectroscopy. The kinetics for the fragmentation of 4 in toluene under CO have been investigated over the temperature range 325-349 K by UV-vis spectroscopy. On the basis of the first-order rate constants and the Eyring activation parameters (ΔH‡ = 25.0(8) kcal/mol; ΔS‡ = -2.6(3) eu), a rate-limiting step involving a polyhedral opening of 4 is supported. 4 is thermally and photochemically sensitive, and reactions conducted in the presence of chlorinated solvents furnish the face-shared bioctahedral compound Cp*Rh(μ-Cl)3Re(CO) 3 (8). Heating 4 and H2S in benzene at ca. 60 °C furnishes the 48e triangular cluster S2Rh3Cp*(CO) 4 (9), which contains two Rh(CO)2 moieties and two face-capping sulfide groups. The reaction of 4 with p-methylbenzenethiol gives the sulfido-bridged dimer Cp*Rh(μSC6H4Me-p) 3Re(CO)3 (11). The dinuclear compounds Cp*Rh(μ-Cl)(μ-SC6H4Me-p)2Re(CO) 3 (10) and 11 are formed when 8 is allowed to react with p-methylbenzenethiol. Treatment of 8 and 10 with excess p-methylbenzenethiol yields 11 at elevated temperature in toluene. Compounds 4-11 have been isolated and fully characterized by IR and NMR spectroscopy and by X-ray crystallography. The reactivity displayed by 4 is contrasted with that of the known indenyl-substituted cluster H2Re2Ir(η5-ind) (CO)9 prepared earlier by Shapley and co-workers.",

author = "Huang, {Shih Huang} and Watson, {William H.} and Carrano, {Carl J.} and Xiaoping Wang and Richmond, {Michael G.}",

year = "2010",

month = jan,

day = "11",

doi = "10.1021/om9007407",

language = "English",

volume = "29",

pages = "61--75",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "1",

}

Directed synthesis of the triangular mixed-metal cluster H ₂RhRe₂Cp*(CO)₉: Ligand fluxionality and facile cluster fragmentation in the presence of CO, halogenated solvents, and thiols. / Huang, Shih Huang; Watson, William H.; Carrano, Carl J. et al.
In: Organometallics, Vol. 29, No. 1, 11.01.2010, p. 61-75.

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

TY - JOUR

T1 - Directed synthesis of the triangular mixed-metal cluster H 2RhRe2Cp*(CO)9

T2 - Ligand fluxionality and facile cluster fragmentation in the presence of CO, halogenated solvents, and thiols

AU - Huang, Shih Huang

AU - Watson, William H.

AU - Carrano, Carl J.

AU - Wang, Xiaoping

AU - Richmond, Michael G.

PY - 2010/1/11

Y1 - 2010/1/11

N2 - The reaction Of H2Re2(CO)8 (1) with Cp*Rh(CO)2 (2) in refluxing hexane affords the mixed-metal clusters H2RhRe2Cp*(CO)9 (4, major product), HRh2ReCp*2(CO)6 (5), and HRhRe3Cp*(CO)14 (6). 4 and 5 are electron-precise 48e clusters and display triangular metallic cores, while 6 contains 64 valence electrons and exhibits a spiked-triangular core having a pendant Re(CO) 5 moiety. Heating 1 with Cp*2Rh2(CO) 2 (3) gives 4 and 5 as the principal products, in addition to H 2Rh2Re2Cp*2(CO)8 (7) in low yield. Cluster 7 possesses 60e and contains a tetrametallic core with two face-capping CO and hydride groups. Heating 4 under CO leads to cluster fragmentation and formation of Re2(CO)io and 2 in essentially quantitative yield, as assessed by IR spectroscopy. The kinetics for the fragmentation of 4 in toluene under CO have been investigated over the temperature range 325-349 K by UV-vis spectroscopy. On the basis of the first-order rate constants and the Eyring activation parameters (ΔH‡ = 25.0(8) kcal/mol; ΔS‡ = -2.6(3) eu), a rate-limiting step involving a polyhedral opening of 4 is supported. 4 is thermally and photochemically sensitive, and reactions conducted in the presence of chlorinated solvents furnish the face-shared bioctahedral compound Cp*Rh(μ-Cl)3Re(CO) 3 (8). Heating 4 and H2S in benzene at ca. 60 °C furnishes the 48e triangular cluster S2Rh3Cp*(CO) 4 (9), which contains two Rh(CO)2 moieties and two face-capping sulfide groups. The reaction of 4 with p-methylbenzenethiol gives the sulfido-bridged dimer Cp*Rh(μSC6H4Me-p) 3Re(CO)3 (11). The dinuclear compounds Cp*Rh(μ-Cl)(μ-SC6H4Me-p)2Re(CO) 3 (10) and 11 are formed when 8 is allowed to react with p-methylbenzenethiol. Treatment of 8 and 10 with excess p-methylbenzenethiol yields 11 at elevated temperature in toluene. Compounds 4-11 have been isolated and fully characterized by IR and NMR spectroscopy and by X-ray crystallography. The reactivity displayed by 4 is contrasted with that of the known indenyl-substituted cluster H2Re2Ir(η5-ind) (CO)9 prepared earlier by Shapley and co-workers.

AB - The reaction Of H2Re2(CO)8 (1) with Cp*Rh(CO)2 (2) in refluxing hexane affords the mixed-metal clusters H2RhRe2Cp*(CO)9 (4, major product), HRh2ReCp*2(CO)6 (5), and HRhRe3Cp*(CO)14 (6). 4 and 5 are electron-precise 48e clusters and display triangular metallic cores, while 6 contains 64 valence electrons and exhibits a spiked-triangular core having a pendant Re(CO) 5 moiety. Heating 1 with Cp*2Rh2(CO) 2 (3) gives 4 and 5 as the principal products, in addition to H 2Rh2Re2Cp*2(CO)8 (7) in low yield. Cluster 7 possesses 60e and contains a tetrametallic core with two face-capping CO and hydride groups. Heating 4 under CO leads to cluster fragmentation and formation of Re2(CO)io and 2 in essentially quantitative yield, as assessed by IR spectroscopy. The kinetics for the fragmentation of 4 in toluene under CO have been investigated over the temperature range 325-349 K by UV-vis spectroscopy. On the basis of the first-order rate constants and the Eyring activation parameters (ΔH‡ = 25.0(8) kcal/mol; ΔS‡ = -2.6(3) eu), a rate-limiting step involving a polyhedral opening of 4 is supported. 4 is thermally and photochemically sensitive, and reactions conducted in the presence of chlorinated solvents furnish the face-shared bioctahedral compound Cp*Rh(μ-Cl)3Re(CO) 3 (8). Heating 4 and H2S in benzene at ca. 60 °C furnishes the 48e triangular cluster S2Rh3Cp*(CO) 4 (9), which contains two Rh(CO)2 moieties and two face-capping sulfide groups. The reaction of 4 with p-methylbenzenethiol gives the sulfido-bridged dimer Cp*Rh(μSC6H4Me-p) 3Re(CO)3 (11). The dinuclear compounds Cp*Rh(μ-Cl)(μ-SC6H4Me-p)2Re(CO) 3 (10) and 11 are formed when 8 is allowed to react with p-methylbenzenethiol. Treatment of 8 and 10 with excess p-methylbenzenethiol yields 11 at elevated temperature in toluene. Compounds 4-11 have been isolated and fully characterized by IR and NMR spectroscopy and by X-ray crystallography. The reactivity displayed by 4 is contrasted with that of the known indenyl-substituted cluster H2Re2Ir(η5-ind) (CO)9 prepared earlier by Shapley and co-workers.

UR - http://www.scopus.com/inward/record.url?scp=73649123132&partnerID=8YFLogxK

U2 - 10.1021/om9007407

DO - 10.1021/om9007407

M3 - Article

AN - SCOPUS:73649123132

SN - 0276-7333

VL - 29

SP - 61

EP - 75

JO - Organometallics

JF - Organometallics

IS - 1

ER -

Directed synthesis of the triangular mixed-metal cluster H ₂RhRe₂Cp*(CO)₉: Ligand fluxionality and facile cluster fragmentation in the presence of CO, halogenated solvents, and thiols

Abstract

Access to Document

Other files and links

Fingerprint

Cite this