Synthesis of Mn(III)X3 (X = Cl, Br, I) Compounds with Phosphine (R3P) Ligands

Sanchita Paul; Ananya Saju; Cooper Cohen; Matthew R. Crawley; Samantha N. MacMillan; David C. Lacy

doi:10.1021/acs.inorgchem.4c01820

Synthesis of Mn(III)X₃ (X = Cl, Br, I) Compounds with Phosphine (R₃P) Ligands

Sanchita Paul
, Ananya Saju
, Cooper Cohen
, Matthew R. Crawley
, Samantha N. MacMillan
, David C. Lacy

Chemistry

SUNY Buffalo
Cornell University

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

7 Scopus citations

Abstract

This work details the synthesis and characterization of complexes of the form [Mn^IIIX₃(PR₃)₂] (X = Cl, Br, I), which is a rare type of coordination compound. Prior to this work, the only mode of synthesis was oxidizing mixtures of Mn^IIX₂ and PR₃ with dry air, but these procedures give low yields and variable outcomes. By taking advantage of the starting material [Mn^IIICl₃(OPPh₃)₂] (1) and other new strategies, we present robust synthetic protocols for both new and known Mn(III) halido phosphine complexes. In addition to [Mn^IIIX₃(PR₃)₂], these include [Mn^IIICl₂(dmpe)₂]⁺ salts and [LMn^IIX₃]⁻ manganates (L = phosphine oxide). Furthermore, the full characterization of these [Mn^IIIX₃(PR₃)₂] species enabled a definitive revisitation of some controversial chemistry surrounding the compounds and products from the dry air oxidation of certain Mn^IIX₂ and phosphine ligand mixtures.

Original language	English
Pages (from-to)	15791-15803
Number of pages	13
Journal	Inorganic Chemistry
Volume	63
Issue number	34
DOIs	https://doi.org/10.1021/acs.inorgchem.4c01820
State	Published - Aug 26 2024

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@article{ad4e91059c3f4d90827e8d059e6f6424,

title = "Synthesis of Mn(III)X3 (X = Cl, Br, I) Compounds with Phosphine (R3P) Ligands",

abstract = "This work details the synthesis and characterization of complexes of the form [MnIIIX3(PR3)2] (X = Cl, Br, I), which is a rare type of coordination compound. Prior to this work, the only mode of synthesis was oxidizing mixtures of MnIIX2 and PR3 with dry air, but these procedures give low yields and variable outcomes. By taking advantage of the starting material [MnIIICl3(OPPh3)2] (1) and other new strategies, we present robust synthetic protocols for both new and known Mn(III) halido phosphine complexes. In addition to [MnIIIX3(PR3)2], these include [MnIIICl2(dmpe)2]+ salts and [LMnIIX3]− manganates (L = phosphine oxide). Furthermore, the full characterization of these [MnIIIX3(PR3)2] species enabled a definitive revisitation of some controversial chemistry surrounding the compounds and products from the dry air oxidation of certain MnIIX2 and phosphine ligand mixtures.",

author = "Sanchita Paul and Ananya Saju and Cooper Cohen and Crawley, \{Matthew R.\} and MacMillan, \{Samantha N.\} and Lacy, \{David C.\}",

note = "Publisher Copyright: {\textcopyright} 2024 American Chemical Society.",

year = "2024",

month = aug,

day = "26",

doi = "10.1021/acs.inorgchem.4c01820",

language = "English",

volume = "63",

pages = "15791--15803",

journal = "Inorganic Chemistry",

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publisher = "American Chemical Society",

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TY - JOUR

T1 - Synthesis of Mn(III)X3 (X = Cl, Br, I) Compounds with Phosphine (R3P) Ligands

AU - Paul, Sanchita

AU - Saju, Ananya

AU - Cohen, Cooper

AU - Crawley, Matthew R.

AU - MacMillan, Samantha N.

AU - Lacy, David C.

PY - 2024/8/26

Y1 - 2024/8/26

N2 - This work details the synthesis and characterization of complexes of the form [MnIIIX3(PR3)2] (X = Cl, Br, I), which is a rare type of coordination compound. Prior to this work, the only mode of synthesis was oxidizing mixtures of MnIIX2 and PR3 with dry air, but these procedures give low yields and variable outcomes. By taking advantage of the starting material [MnIIICl3(OPPh3)2] (1) and other new strategies, we present robust synthetic protocols for both new and known Mn(III) halido phosphine complexes. In addition to [MnIIIX3(PR3)2], these include [MnIIICl2(dmpe)2]+ salts and [LMnIIX3]− manganates (L = phosphine oxide). Furthermore, the full characterization of these [MnIIIX3(PR3)2] species enabled a definitive revisitation of some controversial chemistry surrounding the compounds and products from the dry air oxidation of certain MnIIX2 and phosphine ligand mixtures.

AB - This work details the synthesis and characterization of complexes of the form [MnIIIX3(PR3)2] (X = Cl, Br, I), which is a rare type of coordination compound. Prior to this work, the only mode of synthesis was oxidizing mixtures of MnIIX2 and PR3 with dry air, but these procedures give low yields and variable outcomes. By taking advantage of the starting material [MnIIICl3(OPPh3)2] (1) and other new strategies, we present robust synthetic protocols for both new and known Mn(III) halido phosphine complexes. In addition to [MnIIIX3(PR3)2], these include [MnIIICl2(dmpe)2]+ salts and [LMnIIX3]− manganates (L = phosphine oxide). Furthermore, the full characterization of these [MnIIIX3(PR3)2] species enabled a definitive revisitation of some controversial chemistry surrounding the compounds and products from the dry air oxidation of certain MnIIX2 and phosphine ligand mixtures.

UR - https://www.scopus.com/pages/publications/85201495950

U2 - 10.1021/acs.inorgchem.4c01820

DO - 10.1021/acs.inorgchem.4c01820

M3 - Article

C2 - 39145692

AN - SCOPUS:85201495950

SN - 0020-1669

VL - 63

SP - 15791

EP - 15803

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 34

ER -

Synthesis of Mn(III)X₃ (X = Cl, Br, I) Compounds with Phosphine (R₃P) Ligands

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