Reactivity of dirhenium and triruthenium carbonyls toward a biphosphole ligand: M–M, P–P and C–H bonds cleavage

Abstract:

The reaction of [Re<inf>2</inf>(CO)<inf>8</inf>(CH<inf>3</inf>CN)<inf>2</inf>] with bis(2-thienyl)biphosphole in refluxing n-octane affords the complex [Re(CO)<inf>3</inf>(η⁵-PC<inf>16</inf>H<inf>14</inf>S<inf>2</inf>)] (1) where cleavage of the Re–Re and P–P bonds occurs; its molecular structure confirms the formation of a rhenium mononuclear compound with a η⁵-coordinated phospholyl unit and three carbonyl groups oriented in a tripod. On the other hand, bis(2-thienyl)biphosphole reacts with [Ru<inf>3</inf>(CO)<inf>12</inf>] in refluxing cyclohexane to affording two new compounds [Ru<inf>3</inf>(CO)<inf>9</inf>(μ:η¹:η⁵-PC<inf>16</inf>H<inf>13</inf>S<inf>2</inf>)] (2) and [Ru<inf>4</inf>(CO)<inf>13</inf>(μ:η¹-PC<inf>16</inf>H<inf>14</inf>S<inf>2</inf>)<inf>2</inf>] (3). Spectroscopic data and theoretical studies of 2 suggest the formation of an open Ru3 cluster with two metal–metal bonds bridged by a (η¹:η⁵-PC<inf>16</inf>H<inf>13</inf>S<inf>2</inf>) unit and a C-H bond activation of one of the thienyl substituents. X-ray structure of 3 reveals a novel tetranuclear ruthenium cluster containing 13 terminal carbonyl ligands and two phospholyl units coordinated as μ-phosphide.

Año de publicación:

2017

Keywords:

• Tetranuclear cluster
• Biphosphole
• η -phospholyl complex 5
• Metal-metal and phosphorus-phosphorus bonds cleavage
• η5-phospholyl complex
• C−H Activation

Fuente:

scopus

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