Templated formation of binuclear macrocycles via hemilabile ligands

Joshua R. Farrell; Adam H. Eisenberg; Chad A Mirkin; Ilia A. Guzei; Louise M. Liable-Sands; Christopher D. Incarvito; Arnold L. Rheingold; Charlotte L. Stern

doi:10.1021/om990585+

Templated formation of binuclear macrocycles via hemilabile ligands

Joshua R. Farrell, Adam H. Eisenberg, Chad A Mirkin^*, Ilia A. Guzei, Louise M. Liable-Sands, Christopher D. Incarvito, Arnold L. Rheingold, Charlotte L. Stern

^*Corresponding author for this work

Chemistry

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

48 Scopus citations

Abstract

A new approach to synthesizing binuclear metallomacrocycles is reported. This approach utilizes flexible bisphosphine alkyl-aryl ether hemilabile ligands which complex Rh(I) to form "condensed" macrocycles held together by a series of both strong and weak links of the following type: [(κ²:μ2:κ²-(1,4-(Ph₂PCH ₂CH₂O)₂-2,3,5,6-((CH₃) ₄C₆)))₂Rh₂][BF₄] ₂ (5a) or [(μ²,η¹: η⁶:η¹-(1,4-(Ph₂P(CH₂) _nO)₂-X))₂Rh₂][BF₄] ₂ (5b, n = 2, X = 2,3,5,6-((CH₃)₄C₆); 6, n = 3, X = 2,3,5,6-((CH₃)₄C₆); 7, n = 2, X = C₆H₄; 8, n = 2, X = C₆H₄-C₆H₄). Introduction of ligands that will bind to Rh(I) more strongly than either the Rh-η⁶-aryl or Rh-η¹-ether weak links of 5a-8 results in the breaking of the weak links to form a series of 26-34-membered macrocyclic ring structures such as [(μ²-(1,4-(Ph₂P(CH₂)_nO) ₂X))₂(L₁)_m(L₂) _oRh₂][BF₄]₂ (9, n = 2, X = 2,3,5,6-((CH₃)₄C₆)), L₁ = CO, m = 6, L₂ = none; 10, n = 2, X = C₆H₄, L₁ = CO, m = 6, L₂ = none; 11, n = 2, X= C₆H₄-C₆H₄; L₁ = CO, m = 6, L₂ = none; 12, n = 2, X = 2,3,5,6-((CH₃)₄C₆)), L₁ = CO, m = 2, L₂ = CH₃CN, o = 2; 13, n = 3, X = 2,3,5,6-((CH₃)₄C₆)), L₁ = CO, m = 2, L₂ = CH₃CN, o = 2; 14, n = 2, X = C₆H₄, L₁ = CO, m = 2, L₂ = CH₃CN, o = 2; 15, n = 2, X = C₆H₄-C₆H₄, L₁ = CO, m = 2, L₂ = CH₃CN, o = 2). These homobimetallic macrocycles can be used to sequester bifunctional aromatic molecules to form host-guest structures such as [μ²-(1,4-(Ph₂PCH₂CH₂O) ₂-2,3,5,6-((CH₃)₄C₆))) ₂(CO)₂(μ²-1,4-(-NC)₂C ₆H₄)-Rh₂][BF₄]₂ (16) and [(μ²(1,4-(Ph₂PCH₂CH₂O) ₂-2,3,5,6-((CH₃)₄C₆))) ₂(CH₃CN)₂(μ²-1,4-(-CN) ₂C₆H₄)-Rh₂][BF₄] ₂ (17). The synthetic methods described within this article represent a powerful new way of making binuclear macrocycles from flexible ligands in nearly quantitative yields. Moreover, the macrocycles are highly tailorable with respect to cavity size and hydrophobicity and the metals' steric and electronic environments. Solid-state structures as determined by single-crystal X-ray diffraction studies are presented for compounds 5a, 6, 7, 9, 10, 12, and 17.

Original language	English (US)
Pages (from-to)	4856-4868
Number of pages	13
Journal	Organometallics
Volume	18
Issue number	23
DOIs	https://doi.org/10.1021/om990585+
State	Published - Nov 8 1999

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

Access to Document

10.1021/om990585+

Cite this

@article{cbf05aab0b084f589ce47b418352724c,

title = "Templated formation of binuclear macrocycles via hemilabile ligands",

abstract = "A new approach to synthesizing binuclear metallomacrocycles is reported. This approach utilizes flexible bisphosphine alkyl-aryl ether hemilabile ligands which complex Rh(I) to form {"}condensed{"} macrocycles held together by a series of both strong and weak links of the following type: [(κ2:μ2:κ2-(1,4-(Ph2PCH 2CH2O)2-2,3,5,6-((CH3) 4C6)))2Rh2][BF4] 2 (5a) or [(μ2,η1: η6:η1-(1,4-(Ph2P(CH2) nO)2-X))2Rh2][BF4] 2 (5b, n = 2, X = 2,3,5,6-((CH3)4C6); 6, n = 3, X = 2,3,5,6-((CH3)4C6); 7, n = 2, X = C6H4; 8, n = 2, X = C6H4-C6H4). Introduction of ligands that will bind to Rh(I) more strongly than either the Rh-η6-aryl or Rh-η1-ether weak links of 5a-8 results in the breaking of the weak links to form a series of 26-34-membered macrocyclic ring structures such as [(μ2-(1,4-(Ph2P(CH2)nO) 2X))2(L1)m(L2) oRh2][BF4]2 (9, n = 2, X = 2,3,5,6-((CH3)4C6)), L1 = CO, m = 6, L2 = none; 10, n = 2, X = C6H4, L1 = CO, m = 6, L2 = none; 11, n = 2, X= C6H4-C6H4; L1 = CO, m = 6, L2 = none; 12, n = 2, X = 2,3,5,6-((CH3)4C6)), L1 = CO, m = 2, L2 = CH3CN, o = 2; 13, n = 3, X = 2,3,5,6-((CH3)4C6)), L1 = CO, m = 2, L2 = CH3CN, o = 2; 14, n = 2, X = C6H4, L1 = CO, m = 2, L2 = CH3CN, o = 2; 15, n = 2, X = C6H4-C6H4, L1 = CO, m = 2, L2 = CH3CN, o = 2). These homobimetallic macrocycles can be used to sequester bifunctional aromatic molecules to form host-guest structures such as [μ2-(1,4-(Ph2PCH2CH2O) 2-2,3,5,6-((CH3)4C6))) 2(CO)2(μ2-1,4-(-NC)2C 6H4)-Rh2][BF4]2 (16) and [(μ2(1,4-(Ph2PCH2CH2O) 2-2,3,5,6-((CH3)4C6))) 2(CH3CN)2(μ2-1,4-(-CN) 2C6H4)-Rh2][BF4] 2 (17). The synthetic methods described within this article represent a powerful new way of making binuclear macrocycles from flexible ligands in nearly quantitative yields. Moreover, the macrocycles are highly tailorable with respect to cavity size and hydrophobicity and the metals' steric and electronic environments. Solid-state structures as determined by single-crystal X-ray diffraction studies are presented for compounds 5a, 6, 7, 9, 10, 12, and 17.",

author = "Farrell, {Joshua R.} and Eisenberg, {Adam H.} and Mirkin, {Chad A} and Guzei, {Ilia A.} and Liable-Sands, {Louise M.} and Incarvito, {Christopher D.} and Rheingold, {Arnold L.} and Stern, {Charlotte L.}",

year = "1999",

month = nov,

day = "8",

doi = "10.1021/om990585+",

language = "English (US)",

volume = "18",

pages = "4856--4868",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "23",

}

TY - JOUR

T1 - Templated formation of binuclear macrocycles via hemilabile ligands

AU - Farrell, Joshua R.

AU - Eisenberg, Adam H.

AU - Mirkin, Chad A

AU - Guzei, Ilia A.

AU - Liable-Sands, Louise M.

AU - Incarvito, Christopher D.

AU - Rheingold, Arnold L.

AU - Stern, Charlotte L.

PY - 1999/11/8

Y1 - 1999/11/8

N2 - A new approach to synthesizing binuclear metallomacrocycles is reported. This approach utilizes flexible bisphosphine alkyl-aryl ether hemilabile ligands which complex Rh(I) to form "condensed" macrocycles held together by a series of both strong and weak links of the following type: [(κ2:μ2:κ2-(1,4-(Ph2PCH 2CH2O)2-2,3,5,6-((CH3) 4C6)))2Rh2][BF4] 2 (5a) or [(μ2,η1: η6:η1-(1,4-(Ph2P(CH2) nO)2-X))2Rh2][BF4] 2 (5b, n = 2, X = 2,3,5,6-((CH3)4C6); 6, n = 3, X = 2,3,5,6-((CH3)4C6); 7, n = 2, X = C6H4; 8, n = 2, X = C6H4-C6H4). Introduction of ligands that will bind to Rh(I) more strongly than either the Rh-η6-aryl or Rh-η1-ether weak links of 5a-8 results in the breaking of the weak links to form a series of 26-34-membered macrocyclic ring structures such as [(μ2-(1,4-(Ph2P(CH2)nO) 2X))2(L1)m(L2) oRh2][BF4]2 (9, n = 2, X = 2,3,5,6-((CH3)4C6)), L1 = CO, m = 6, L2 = none; 10, n = 2, X = C6H4, L1 = CO, m = 6, L2 = none; 11, n = 2, X= C6H4-C6H4; L1 = CO, m = 6, L2 = none; 12, n = 2, X = 2,3,5,6-((CH3)4C6)), L1 = CO, m = 2, L2 = CH3CN, o = 2; 13, n = 3, X = 2,3,5,6-((CH3)4C6)), L1 = CO, m = 2, L2 = CH3CN, o = 2; 14, n = 2, X = C6H4, L1 = CO, m = 2, L2 = CH3CN, o = 2; 15, n = 2, X = C6H4-C6H4, L1 = CO, m = 2, L2 = CH3CN, o = 2). These homobimetallic macrocycles can be used to sequester bifunctional aromatic molecules to form host-guest structures such as [μ2-(1,4-(Ph2PCH2CH2O) 2-2,3,5,6-((CH3)4C6))) 2(CO)2(μ2-1,4-(-NC)2C 6H4)-Rh2][BF4]2 (16) and [(μ2(1,4-(Ph2PCH2CH2O) 2-2,3,5,6-((CH3)4C6))) 2(CH3CN)2(μ2-1,4-(-CN) 2C6H4)-Rh2][BF4] 2 (17). The synthetic methods described within this article represent a powerful new way of making binuclear macrocycles from flexible ligands in nearly quantitative yields. Moreover, the macrocycles are highly tailorable with respect to cavity size and hydrophobicity and the metals' steric and electronic environments. Solid-state structures as determined by single-crystal X-ray diffraction studies are presented for compounds 5a, 6, 7, 9, 10, 12, and 17.

AB - A new approach to synthesizing binuclear metallomacrocycles is reported. This approach utilizes flexible bisphosphine alkyl-aryl ether hemilabile ligands which complex Rh(I) to form "condensed" macrocycles held together by a series of both strong and weak links of the following type: [(κ2:μ2:κ2-(1,4-(Ph2PCH 2CH2O)2-2,3,5,6-((CH3) 4C6)))2Rh2][BF4] 2 (5a) or [(μ2,η1: η6:η1-(1,4-(Ph2P(CH2) nO)2-X))2Rh2][BF4] 2 (5b, n = 2, X = 2,3,5,6-((CH3)4C6); 6, n = 3, X = 2,3,5,6-((CH3)4C6); 7, n = 2, X = C6H4; 8, n = 2, X = C6H4-C6H4). Introduction of ligands that will bind to Rh(I) more strongly than either the Rh-η6-aryl or Rh-η1-ether weak links of 5a-8 results in the breaking of the weak links to form a series of 26-34-membered macrocyclic ring structures such as [(μ2-(1,4-(Ph2P(CH2)nO) 2X))2(L1)m(L2) oRh2][BF4]2 (9, n = 2, X = 2,3,5,6-((CH3)4C6)), L1 = CO, m = 6, L2 = none; 10, n = 2, X = C6H4, L1 = CO, m = 6, L2 = none; 11, n = 2, X= C6H4-C6H4; L1 = CO, m = 6, L2 = none; 12, n = 2, X = 2,3,5,6-((CH3)4C6)), L1 = CO, m = 2, L2 = CH3CN, o = 2; 13, n = 3, X = 2,3,5,6-((CH3)4C6)), L1 = CO, m = 2, L2 = CH3CN, o = 2; 14, n = 2, X = C6H4, L1 = CO, m = 2, L2 = CH3CN, o = 2; 15, n = 2, X = C6H4-C6H4, L1 = CO, m = 2, L2 = CH3CN, o = 2). These homobimetallic macrocycles can be used to sequester bifunctional aromatic molecules to form host-guest structures such as [μ2-(1,4-(Ph2PCH2CH2O) 2-2,3,5,6-((CH3)4C6))) 2(CO)2(μ2-1,4-(-NC)2C 6H4)-Rh2][BF4]2 (16) and [(μ2(1,4-(Ph2PCH2CH2O) 2-2,3,5,6-((CH3)4C6))) 2(CH3CN)2(μ2-1,4-(-CN) 2C6H4)-Rh2][BF4] 2 (17). The synthetic methods described within this article represent a powerful new way of making binuclear macrocycles from flexible ligands in nearly quantitative yields. Moreover, the macrocycles are highly tailorable with respect to cavity size and hydrophobicity and the metals' steric and electronic environments. Solid-state structures as determined by single-crystal X-ray diffraction studies are presented for compounds 5a, 6, 7, 9, 10, 12, and 17.

UR - http://www.scopus.com/inward/record.url?scp=0000300204&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0000300204&partnerID=8YFLogxK

U2 - 10.1021/om990585+

DO - 10.1021/om990585+

M3 - Article

AN - SCOPUS:0000300204

SN - 0276-7333

VL - 18

SP - 4856

EP - 4868

JO - Organometallics

JF - Organometallics

IS - 23

ER -

Templated formation of binuclear macrocycles via hemilabile ligands

Abstract

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

CCDC 109386: Experimental Crystal Structure Determination

CCDC 140626: Experimental Crystal Structure Determination

CCDC 140623: Experimental Crystal Structure Determination

Cite this

Templated formation of binuclear macrocycles via hemilabile ligands

Abstract

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Datasets

CCDC 109386: Experimental Crystal Structure Determination

CCDC 140626: Experimental Crystal Structure Determination

CCDC 140623: Experimental Crystal Structure Determination

Cite this