Aqueous polymerization of styrene promoted by water-soluble robust ruthenium hydride complexes

Seiji Ogo; Keiji Uehara; Tsutomu Abura; Yoshihito Watanabe; Shunichi Fukuzumi

doi:10.1021/om034335b

Aqueous polymerization of styrene promoted by water-soluble robust ruthenium hydride complexes

Seiji Ogo, Keiji Uehara, Tsutomu Abura, Yoshihito Watanabe, Shunichi Fukuzumi

Department of Chemistry & Nanoscience

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

53 Scopus citations

Abstract

Aqueous polymerization of styrene in biphasic media (styrene/water) has been achieved by water-soluble robust mononuclear hydride complexes [(ν⁶-C₆Me₆)Ru^II(bpy)H] _n(X) {[1]_n(X), where X = SO₄ (n = 2) or CF ₃SO₃ (n = 1), bpy = 2,2′-bipyridine}. The hydride complex [1]₂(SO₄) was synthesized from the reaction of an aqua complex [(ν⁶-C₆Me₆)Ru^II. (bpy)(H₂O)](SO₄) {2(SO₄)} with a water-soluble hydrogen donor HCOONa in H₂O in a pH range of 4-12 at 70-100°C. The structures of [1]₂(SO₄) and 1(CF₃SO ₃) were determined by X-ray analysis, ¹H and ²H NMR, IR, and electrospray ionization mass spectrometry (ESI-MS). X-ray analysis has revealed that complex 1(CF₃SO₃) adopts a distorted octahedral geometry with the Ru atom coordinated by one ν⁶-C ₆Me₆ ligand, one bidentate bpy ligand, and one terminal hydrido ligand that occupies a bond position. Complex [1]₂(SO ₄) reacts with excess amounts of styrene in biphasic media to provide polystyrene in a 62% isolated yield for 8 h. The polydispersity (M _w/M_n) of the obtained polystyrene is 1.8. The isolated yield of polystyrene shows a maximum around pH 8. The pH-dependence is similar to the pH-dependent formation of 1. Growing polymer intermediates [(C ₆Me₆)Ru(bpy){(C₂H₃)-(C ₆H₅)}_nH]⁺ (n = 1-4) were directly observed by ESI-MS.

Original language	English
Pages (from-to)	3047-3052
Number of pages	6
Journal	Organometallics
Volume	23
Issue number	12
DOIs	https://doi.org/10.1021/om034335b
State	Published - 7 Jun 2004

Access to Document

10.1021/om034335b

Cite this

@article{46ae0364fc2246868b32fb8596094843,

title = "Aqueous polymerization of styrene promoted by water-soluble robust ruthenium hydride complexes",

abstract = "Aqueous polymerization of styrene in biphasic media (styrene/water) has been achieved by water-soluble robust mononuclear hydride complexes [(ν6-C6Me6)RuII(bpy)H] n(X) {[1]n(X), where X = SO4 (n = 2) or CF 3SO3 (n = 1), bpy = 2,2′-bipyridine}. The hydride complex [1]2(SO4) was synthesized from the reaction of an aqua complex [(ν6-C6Me6)RuII. (bpy)(H2O)](SO4) {2(SO4)} with a water-soluble hydrogen donor HCOONa in H2O in a pH range of 4-12 at 70-100°C. The structures of [1]2(SO4) and 1(CF3SO 3) were determined by X-ray analysis, 1H and 2H NMR, IR, and electrospray ionization mass spectrometry (ESI-MS). X-ray analysis has revealed that complex 1(CF3SO3) adopts a distorted octahedral geometry with the Ru atom coordinated by one ν6-C 6Me6 ligand, one bidentate bpy ligand, and one terminal hydrido ligand that occupies a bond position. Complex [1]2(SO 4) reacts with excess amounts of styrene in biphasic media to provide polystyrene in a 62% isolated yield for 8 h. The polydispersity (M w/Mn) of the obtained polystyrene is 1.8. The isolated yield of polystyrene shows a maximum around pH 8. The pH-dependence is similar to the pH-dependent formation of 1. Growing polymer intermediates [(C 6Me6)Ru(bpy){(C2H3)-(C 6H5)}nH]+ (n = 1-4) were directly observed by ESI-MS.",

author = "Seiji Ogo and Keiji Uehara and Tsutomu Abura and Yoshihito Watanabe and Shunichi Fukuzumi",

year = "2004",

month = jun,

day = "7",

doi = "10.1021/om034335b",

language = "English",

volume = "23",

pages = "3047--3052",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "12",

}

TY - JOUR

T1 - Aqueous polymerization of styrene promoted by water-soluble robust ruthenium hydride complexes

AU - Ogo, Seiji

AU - Uehara, Keiji

AU - Abura, Tsutomu

AU - Watanabe, Yoshihito

AU - Fukuzumi, Shunichi

PY - 2004/6/7

Y1 - 2004/6/7

N2 - Aqueous polymerization of styrene in biphasic media (styrene/water) has been achieved by water-soluble robust mononuclear hydride complexes [(ν6-C6Me6)RuII(bpy)H] n(X) {[1]n(X), where X = SO4 (n = 2) or CF 3SO3 (n = 1), bpy = 2,2′-bipyridine}. The hydride complex [1]2(SO4) was synthesized from the reaction of an aqua complex [(ν6-C6Me6)RuII. (bpy)(H2O)](SO4) {2(SO4)} with a water-soluble hydrogen donor HCOONa in H2O in a pH range of 4-12 at 70-100°C. The structures of [1]2(SO4) and 1(CF3SO 3) were determined by X-ray analysis, 1H and 2H NMR, IR, and electrospray ionization mass spectrometry (ESI-MS). X-ray analysis has revealed that complex 1(CF3SO3) adopts a distorted octahedral geometry with the Ru atom coordinated by one ν6-C 6Me6 ligand, one bidentate bpy ligand, and one terminal hydrido ligand that occupies a bond position. Complex [1]2(SO 4) reacts with excess amounts of styrene in biphasic media to provide polystyrene in a 62% isolated yield for 8 h. The polydispersity (M w/Mn) of the obtained polystyrene is 1.8. The isolated yield of polystyrene shows a maximum around pH 8. The pH-dependence is similar to the pH-dependent formation of 1. Growing polymer intermediates [(C 6Me6)Ru(bpy){(C2H3)-(C 6H5)}nH]+ (n = 1-4) were directly observed by ESI-MS.

AB - Aqueous polymerization of styrene in biphasic media (styrene/water) has been achieved by water-soluble robust mononuclear hydride complexes [(ν6-C6Me6)RuII(bpy)H] n(X) {[1]n(X), where X = SO4 (n = 2) or CF 3SO3 (n = 1), bpy = 2,2′-bipyridine}. The hydride complex [1]2(SO4) was synthesized from the reaction of an aqua complex [(ν6-C6Me6)RuII. (bpy)(H2O)](SO4) {2(SO4)} with a water-soluble hydrogen donor HCOONa in H2O in a pH range of 4-12 at 70-100°C. The structures of [1]2(SO4) and 1(CF3SO 3) were determined by X-ray analysis, 1H and 2H NMR, IR, and electrospray ionization mass spectrometry (ESI-MS). X-ray analysis has revealed that complex 1(CF3SO3) adopts a distorted octahedral geometry with the Ru atom coordinated by one ν6-C 6Me6 ligand, one bidentate bpy ligand, and one terminal hydrido ligand that occupies a bond position. Complex [1]2(SO 4) reacts with excess amounts of styrene in biphasic media to provide polystyrene in a 62% isolated yield for 8 h. The polydispersity (M w/Mn) of the obtained polystyrene is 1.8. The isolated yield of polystyrene shows a maximum around pH 8. The pH-dependence is similar to the pH-dependent formation of 1. Growing polymer intermediates [(C 6Me6)Ru(bpy){(C2H3)-(C 6H5)}nH]+ (n = 1-4) were directly observed by ESI-MS.

UR - http://www.scopus.com/inward/record.url?scp=2942746791&partnerID=8YFLogxK

U2 - 10.1021/om034335b

DO - 10.1021/om034335b

M3 - Article

AN - SCOPUS:2942746791

SN - 0276-7333

VL - 23

SP - 3047

EP - 3052

JO - Organometallics

JF - Organometallics

IS - 12

ER -

Aqueous polymerization of styrene promoted by water-soluble robust ruthenium hydride complexes

Abstract

Access to Document

Fingerprint

Cite this