Square planar Ru(iPr2PCH2CH2NH)2 and its role in fast and selective catalytic amine–borane dehydropolymerization to form high molecular weight polyaminoboranes

Mathew J. Cross; M. Arif Sajjad; Stuart A. Macgregor; Andrew S. Weller

doi:10.1002/anie.202500019

Square planar Ru(ⁱPr₂PCH₂CH₂NH)₂ and its role in fast and selective catalytic amine–borane dehydropolymerization to form high molecular weight polyaminoboranes

Mathew J. Cross
, M. Arif Sajjad
, Stuart A. Macgregor
, Andrew S. Weller

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

Abstract

Addition of ^tBuOK to orange RuCl₂(ⁱPr₂PCH₂CH₂NH₂)₂ forms the pink, square planar, Ru(II) complex Ru(ⁱPr₂PCH₂CH₂NH)₂ . This is an active catalyst (ToF 250 s⁻¹) for the dehydropolymerization of H₃B·NMeH₂ to give high molecular weight polyaminoborane, [H₂BNMeH]n (M_n = 138 700 g mol⁻¹) at low loadings (0.03 mol%). An induction period observed is due to the initial formation of a hydroxy-hydride species, Ru(ⁱPr₂PCH₂CH₂NH)₂ (OH)(H), prior to fast turnover.

Original language	English
Article number	e202500019
Journal	Angewandte Chemie
Volume	64
Issue number	24
Early online date	17 Apr 2025
DOIs	https://doi.org/10.1002/anie.202500019
Publication status	Published - 10 Jun 2025

Keywords

Amine–borane dehydropolymerization
Catalysis
Cooperative ligands
DFT
Mechanism

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@article{53d0bb185cad420dabbd85f489a67eda,

title = "Square planar Ru(iPr2PCH2CH2NH)2 and its role in fast and selective catalytic amine–borane dehydropolymerization to form high molecular weight polyaminoboranes",

abstract = "Addition of tBuOK to orange RuCl2(iPr2PCH2CH2NH2)2 forms the pink, square planar, Ru(II) complex Ru(iPr2PCH2CH2NH)2 . This is an active catalyst (ToF 250 s−1) for the dehydropolymerization of H3B·NMeH2 to give high molecular weight polyaminoborane, [H2BNMeH]n (Mn = 138 700 g mol−1) at low loadings (0.03 mol\%). An induction period observed is due to the initial formation of a hydroxy-hydride species, Ru(iPr2PCH2CH2NH)2 (OH)(H), prior to fast turnover.",

keywords = "Amine–borane dehydropolymerization, Catalysis, Cooperative ligands, DFT, Mechanism",

author = "Cross, \{Mathew J.\} and Sajjad, \{M. Arif\} and Macgregor, \{Stuart A.\} and Weller, \{Andrew S.\}",

note = "Funding: The University of York (MJC), EPSRC (EP/W015498/2, SAM) for funding.",

year = "2025",

month = jun,

day = "10",

doi = "10.1002/anie.202500019",

language = "English",

volume = "64",

journal = "Angewandte Chemie",

issn = "0044-8249",

publisher = "John Wiley \& Sons, Ltd",

number = "24",

}

TY - JOUR

T1 - Square planar Ru(iPr2PCH2CH2NH)2 and its role in fast and selective catalytic amine–borane dehydropolymerization to form high molecular weight polyaminoboranes

AU - Cross, Mathew J.

AU - Sajjad, M. Arif

AU - Macgregor, Stuart A.

AU - Weller, Andrew S.

N1 - Funding: The University of York (MJC), EPSRC (EP/W015498/2, SAM) for funding.

PY - 2025/6/10

Y1 - 2025/6/10

N2 - Addition of tBuOK to orange RuCl2(iPr2PCH2CH2NH2)2 forms the pink, square planar, Ru(II) complex Ru(iPr2PCH2CH2NH)2 . This is an active catalyst (ToF 250 s−1) for the dehydropolymerization of H3B·NMeH2 to give high molecular weight polyaminoborane, [H2BNMeH]n (Mn = 138 700 g mol−1) at low loadings (0.03 mol%). An induction period observed is due to the initial formation of a hydroxy-hydride species, Ru(iPr2PCH2CH2NH)2 (OH)(H), prior to fast turnover.

AB - Addition of tBuOK to orange RuCl2(iPr2PCH2CH2NH2)2 forms the pink, square planar, Ru(II) complex Ru(iPr2PCH2CH2NH)2 . This is an active catalyst (ToF 250 s−1) for the dehydropolymerization of H3B·NMeH2 to give high molecular weight polyaminoborane, [H2BNMeH]n (Mn = 138 700 g mol−1) at low loadings (0.03 mol%). An induction period observed is due to the initial formation of a hydroxy-hydride species, Ru(iPr2PCH2CH2NH)2 (OH)(H), prior to fast turnover.

KW - Amine–borane dehydropolymerization

KW - Catalysis

KW - Cooperative ligands

KW - DFT

KW - Mechanism

U2 - 10.1002/anie.202500019

DO - 10.1002/anie.202500019

M3 - Article

SN - 0044-8249

VL - 64

JO - Angewandte Chemie

JF - Angewandte Chemie

IS - 24

M1 - e202500019

ER -