Reversible, Electrochemically Controlled Binding of Phosphine to Iron and Cobalt Bis(dithiolene) Complexes

The homoleptic bis(dithiolene) complexes [M(S2C2R2)2]2 (M = Fe, Co; R = p-anisyl) undergo two successive reductions to form anions that display [M(S2C2R2)2]22- ↔ 2[M(S2C2R2)2]1- solution equilibria. The neutral dimers react with Ph3P to form square pyramidal [M(Ph3P)(S2C2R2)2]0. Voltammetric measurements upon [M(Ph3P)(S2C2R2)2]0 in CH2Cl2 reveal only irreversible features at negative potentials, consistent with Ph3P dissociation upon reduction. Dissociation and reassociation of Ph3P from and to [Fe(Ph3P)(S2C2R2)2]0 is demonstrated by spectroelectrochemical measurements. These collective observations form the basis for a cycle of reversible, electrochemically controlled binding of Ph3P to [M(S2C2R2)2]2 (M = Fe, Co; R = p-anisyl). All members of the cycle ([M(S2C2R2)2]20, [M(S2C2R2)2]21-, [M(S2C2R2)2]22-, [M(S2C2R2)2]1-, [M(Ph3P)(S2C2R2)2]) for M = Fe, Co have been characterized by crystallography. Square planar [Fe(S2C2R2)2]1- is the first such iron dithiolene species to be structurally identified and reveals Fe−S bond distances of 2.172(1) and 2.179(1) Å, which are appreciably shorter than those in corresponding square planar dianions

Reversible, Electrochemically Controlled Binding of Phosphine to Iron and Cobalt Bis(dithiolene) Complexes

The homoleptic bis(dithiolene) complexes [M(S2C2R2)2]2 (M = Fe, Co; R = p-anisyl) undergo two successive reductions to form anions that display [M(S2C2R2)2]22- ↔ 2[M(S2C2R2)2]1- solution equilibria. The neutral dimers react with Ph3P to form square pyramidal [M(Ph3P)(S2C2R2)2]0. Voltammetric measurements upon [M(Ph3P)(S2C2R2)2]0 in CH2Cl2 reveal only irreversible features at negative potentials, consistent with Ph3P dissociation upon reduction. Dissociation and reassociation of Ph3P from and to [Fe(Ph3P)(S2C2R2)2]0 is demonstrated by spectroelectrochemical measurements. These collective observations form the basis for a cycle of reversible, electrochemically controlled binding of Ph3P to [M(S2C2R2)2]2 (M = Fe, Co; R = p-anisyl). All members of the cycle ([M(S2C2R2)2]20, [M(S2C2R2)2]21-, [M(S2C2R2)2]22-, [M(S2C2R2)2]1-, [M(Ph3P)(S2C2R2)2]) for M = Fe, Co have been characterized by crystallography. Square planar [Fe(S2C2R2)2]1- is the first such iron dithiolene species to be structurally identified and reveals Fe−S bond distances of 2.172(1) and 2.179(1) Å, which are appreciably shorter than those in corresponding square planar dianions

Reversible, Electrochemically Controlled Binding of Phosphine to Iron and Cobalt Bis(dithiolene) Complexes

The homoleptic bis(dithiolene) complexes [M(S2C2R2)2]2 (M = Fe, Co; R = p-anisyl) undergo two successive reductions to form anions that display [M(S2C2R2)2]22- ↔ 2[M(S2C2R2)2]1- solution equilibria. The neutral dimers react with Ph3P to form square pyramidal [M(Ph3P)(S2C2R2)2]0. Voltammetric measurements upon [M(Ph3P)(S2C2R2)2]0 in CH2Cl2 reveal only irreversible features at negative potentials, consistent with Ph3P dissociation upon reduction. Dissociation and reassociation of Ph3P from and to [Fe(Ph3P)(S2C2R2)2]0 is demonstrated by spectroelectrochemical measurements. These collective observations form the basis for a cycle of reversible, electrochemically controlled binding of Ph3P to [M(S2C2R2)2]2 (M = Fe, Co; R = p-anisyl). All members of the cycle ([M(S2C2R2)2]20, [M(S2C2R2)2]21-, [M(S2C2R2)2]22-, [M(S2C2R2)2]1-, [M(Ph3P)(S2C2R2)2]) for M = Fe, Co have been characterized by crystallography. Square planar [Fe(S2C2R2)2]1- is the first such iron dithiolene species to be structurally identified and reveals Fe−S bond distances of 2.172(1) and 2.179(1) Å, which are appreciably shorter than those in corresponding square planar dianions

Reversible, Electrochemically Controlled Binding of Phosphine to Iron and Cobalt Bis(dithiolene) Complexes

The homoleptic bis(dithiolene) complexes [M(S2C2R2)2]2 (M = Fe, Co; R = p-anisyl) undergo two successive reductions to form anions that display [M(S2C2R2)2]22- ↔ 2[M(S2C2R2)2]1- solution equilibria. The neutral dimers react with Ph3P to form square pyramidal [M(Ph3P)(S2C2R2)2]0. Voltammetric measurements upon [M(Ph3P)(S2C2R2)2]0 in CH2Cl2 reveal only irreversible features at negative potentials, consistent with Ph3P dissociation upon reduction. Dissociation and reassociation of Ph3P from and to [Fe(Ph3P)(S2C2R2)2]0 is demonstrated by spectroelectrochemical measurements. These collective observations form the basis for a cycle of reversible, electrochemically controlled binding of Ph3P to [M(S2C2R2)2]2 (M = Fe, Co; R = p-anisyl). All members of the cycle ([M(S2C2R2)2]20, [M(S2C2R2)2]21-, [M(S2C2R2)2]22-, [M(S2C2R2)2]1-, [M(Ph3P)(S2C2R2)2]) for M = Fe, Co have been characterized by crystallography. Square planar [Fe(S2C2R2)2]1- is the first such iron dithiolene species to be structurally identified and reveals Fe−S bond distances of 2.172(1) and 2.179(1) Å, which are appreciably shorter than those in corresponding square planar dianions

Reversible, Electrochemically Controlled Binding of Phosphine to Iron and Cobalt Bis(dithiolene) Complexes

The homoleptic bis(dithiolene) complexes [M(S2C2R2)2]2 (M = Fe, Co; R = p-anisyl) undergo two successive reductions to form anions that display [M(S2C2R2)2]22- ↔ 2[M(S2C2R2)2]1- solution equilibria. The neutral dimers react with Ph3P to form square pyramidal [M(Ph3P)(S2C2R2)2]0. Voltammetric measurements upon [M(Ph3P)(S2C2R2)2]0 in CH2Cl2 reveal only irreversible features at negative potentials, consistent with Ph3P dissociation upon reduction. Dissociation and reassociation of Ph3P from and to [Fe(Ph3P)(S2C2R2)2]0 is demonstrated by spectroelectrochemical measurements. These collective observations form the basis for a cycle of reversible, electrochemically controlled binding of Ph3P to [M(S2C2R2)2]2 (M = Fe, Co; R = p-anisyl). All members of the cycle ([M(S2C2R2)2]20, [M(S2C2R2)2]21-, [M(S2C2R2)2]22-, [M(S2C2R2)2]1-, [M(Ph3P)(S2C2R2)2]) for M = Fe, Co have been characterized by crystallography. Square planar [Fe(S2C2R2)2]1- is the first such iron dithiolene species to be structurally identified and reveals Fe−S bond distances of 2.172(1) and 2.179(1) Å, which are appreciably shorter than those in corresponding square planar dianions

Reversible, Electrochemically Controlled Binding of Phosphine to Iron and Cobalt Bis(dithiolene) Complexes

The homoleptic bis(dithiolene) complexes [M(S2C2R2)2]2 (M = Fe, Co; R = p-anisyl) undergo two successive reductions to form anions that display [M(S2C2R2)2]22- ↔ 2[M(S2C2R2)2]1- solution equilibria. The neutral dimers react with Ph3P to form square pyramidal [M(Ph3P)(S2C2R2)2]0. Voltammetric measurements upon [M(Ph3P)(S2C2R2)2]0 in CH2Cl2 reveal only irreversible features at negative potentials, consistent with Ph3P dissociation upon reduction. Dissociation and reassociation of Ph3P from and to [Fe(Ph3P)(S2C2R2)2]0 is demonstrated by spectroelectrochemical measurements. These collective observations form the basis for a cycle of reversible, electrochemically controlled binding of Ph3P to [M(S2C2R2)2]2 (M = Fe, Co; R = p-anisyl). All members of the cycle ([M(S2C2R2)2]20, [M(S2C2R2)2]21-, [M(S2C2R2)2]22-, [M(S2C2R2)2]1-, [M(Ph3P)(S2C2R2)2]) for M = Fe, Co have been characterized by crystallography. Square planar [Fe(S2C2R2)2]1- is the first such iron dithiolene species to be structurally identified and reveals Fe−S bond distances of 2.172(1) and 2.179(1) Å, which are appreciably shorter than those in corresponding square planar dianions