Transition Metal Methylene Complexes. 36. Chelate-Type Bridging α-Diazo Ketones through Cleavage of a Metal-Metal Triple Bond

Linda K. Bell; Wolfgang A. Herrmann; Manfred L. Ziegler; Heike Pfisterer

doi:10.1021/om00072a024

Transition Metal Methylene Complexes. 36. Chelate-Type Bridging α-Diazo Ketones through Cleavage of a Metal-Metal Triple Bond

Linda K. Bell, Wolfgang A. Herrmann, Manfred L. Ziegler, Heike Pfisterer

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16 Scopus citations

Abstract

Cleavage of the metal-metal triple bond of bis[dicarbonyl(η⁵-pentamethylcyclopentadienyl)molybdenum](Mo≡Mo) (1a) is effected by the α-ketodiazoalkanes 2a-d resulting in the formation of the chelate-type dinuclear insertion products 3a-d. An X-ray crystallographic study of the key compound 3a revealed the central structural frame [formula omitted] to be composed of an essentially planar five-membered metallacyclic unit that coordinates to the second metal atom via a terminal nitrogen group (Mo(2)−N(2) = 183.6 (17) pm; N(1)−N(2) = 124.4 (24) pm). No molybdenum-molybdenum bond is present after α-diazo ketone addition to the unsaturated organometallic precursor 1a, with the nonbonding MoMo distance being longer than 380 pm. Metal-metal bond cleavage appears to be prevalent in the reactions of metal-metal triple bonds with carbonyl-flanked diazoalkanes capable of chelating mononuclear organometallic fragments.

Original language	English
Pages (from-to)	1673-1678
Number of pages	6
Journal	Organometallics
Volume	1
Issue number	12
DOIs	https://doi.org/10.1021/om00072a024
State	Published - 1982
Externally published	Yes

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title = "Transition Metal Methylene Complexes. 36. Chelate-Type Bridging α-Diazo Ketones through Cleavage of a Metal-Metal Triple Bond",

abstract = "Cleavage of the metal-metal triple bond of bis[dicarbonyl(η5-pentamethylcyclopentadienyl)molybdenum](Mo≡Mo) (1a) is effected by the α-ketodiazoalkanes 2a-d resulting in the formation of the chelate-type dinuclear insertion products 3a-d. An X-ray crystallographic study of the key compound 3a revealed the central structural frame [formula omitted] to be composed of an essentially planar five-membered metallacyclic unit that coordinates to the second metal atom via a terminal nitrogen group (Mo(2)−N(2) = 183.6 (17) pm; N(1)−N(2) = 124.4 (24) pm). No molybdenum-molybdenum bond is present after α-diazo ketone addition to the unsaturated organometallic precursor 1a, with the nonbonding MoMo distance being longer than 380 pm. Metal-metal bond cleavage appears to be prevalent in the reactions of metal-metal triple bonds with carbonyl-flanked diazoalkanes capable of chelating mononuclear organometallic fragments.",

author = "Bell, {Linda K.} and Herrmann, {Wolfgang A.} and Ziegler, {Manfred L.} and Heike Pfisterer",

year = "1982",

doi = "10.1021/om00072a024",

language = "English",

volume = "1",

pages = "1673--1678",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "12",

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TY - JOUR

T1 - Transition Metal Methylene Complexes. 36. Chelate-Type Bridging α-Diazo Ketones through Cleavage of a Metal-Metal Triple Bond

AU - Bell, Linda K.

AU - Herrmann, Wolfgang A.

AU - Ziegler, Manfred L.

AU - Pfisterer, Heike

PY - 1982

Y1 - 1982

N2 - Cleavage of the metal-metal triple bond of bis[dicarbonyl(η5-pentamethylcyclopentadienyl)molybdenum](Mo≡Mo) (1a) is effected by the α-ketodiazoalkanes 2a-d resulting in the formation of the chelate-type dinuclear insertion products 3a-d. An X-ray crystallographic study of the key compound 3a revealed the central structural frame [formula omitted] to be composed of an essentially planar five-membered metallacyclic unit that coordinates to the second metal atom via a terminal nitrogen group (Mo(2)−N(2) = 183.6 (17) pm; N(1)−N(2) = 124.4 (24) pm). No molybdenum-molybdenum bond is present after α-diazo ketone addition to the unsaturated organometallic precursor 1a, with the nonbonding MoMo distance being longer than 380 pm. Metal-metal bond cleavage appears to be prevalent in the reactions of metal-metal triple bonds with carbonyl-flanked diazoalkanes capable of chelating mononuclear organometallic fragments.

AB - Cleavage of the metal-metal triple bond of bis[dicarbonyl(η5-pentamethylcyclopentadienyl)molybdenum](Mo≡Mo) (1a) is effected by the α-ketodiazoalkanes 2a-d resulting in the formation of the chelate-type dinuclear insertion products 3a-d. An X-ray crystallographic study of the key compound 3a revealed the central structural frame [formula omitted] to be composed of an essentially planar five-membered metallacyclic unit that coordinates to the second metal atom via a terminal nitrogen group (Mo(2)−N(2) = 183.6 (17) pm; N(1)−N(2) = 124.4 (24) pm). No molybdenum-molybdenum bond is present after α-diazo ketone addition to the unsaturated organometallic precursor 1a, with the nonbonding MoMo distance being longer than 380 pm. Metal-metal bond cleavage appears to be prevalent in the reactions of metal-metal triple bonds with carbonyl-flanked diazoalkanes capable of chelating mononuclear organometallic fragments.

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U2 - 10.1021/om00072a024

DO - 10.1021/om00072a024

M3 - Article

AN - SCOPUS:38649127612

SN - 0276-7333

VL - 1

SP - 1673

EP - 1678

JO - Organometallics

JF - Organometallics

IS - 12

ER -

Transition Metal Methylene Complexes. 36. Chelate-Type Bridging α-Diazo Ketones through Cleavage of a Metal-Metal Triple Bond

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