Chemistry at the Sterically Shielded Mercury Centre of the [(η4-pp3)PtHg] Fragment

Abstract

Treatment of [(η 4 -pp3)PtH]OTf (pp3 = tris[2-(diphenylphosphanyl)ethyl]phosphane) with PhHgCl gave [(η 4 -pp3)-PtHgCl]OTf (1a) in good yield. The reaction of 1a with the carbonylmetallates [Mn(CO) 5 ] − or [Co(CO) 4 ] − and TlOTf produced the linear trinuclear clusters [(η 4 -pp3)-PtHgMn(CO) 5 ]OTf (2) or [(η 4 -pp3)PtHgCo(CO) 4 ]OTf (3), respectively. The reaction of 1a with PR 3 and TlOTf gave [(η 4 -pp3)PtHg(PR 3 )](OTf) 2 (4: R = nBu; 5: R = Ph), with Ph 2 P(CH 2 ) n PPh 2 (n = 1, 2) or dppmSe [dppmSe = bis(diphenylphosphanyl)methane monoselenide] adducts in which the diphosphane/diphosphane monoselenide adopts a mono-

Bis(2,6-dinitroaryl)platinum Complexes. 2.1 Di- and Trinuclear Complexes Containing Pt−Hg Bonds

“…The two Pt−Hg bond distances are somewhat different in complex 7 [2.6093(3), 2.5914(3) Å], although Hg is trans to the same ligand, and are slightly longer than that in 9 [2.5898(2) Å]. These Pt−Hg distances lie in the range reported in other complexes containing covalent Pt−Hg bonds (2.666−2.513 Å), ,− but they are shorter than those in other complexes in which a metal−metal bond was described as Pt → Hg or could be thus formulated (2.835−2.650 Å) 4,5,14,15 or in higher nuclearity clusters (3.159−2.671 Å). , The Ar groups are bonded to platinum as chelating ligands and are mutually cis . The four Pt−C distances in 7 are not significantly different [range 2.024(5)−2.008(5) Å], but in 9 , they are slightly different [1.989(4), 2.018(4) Å].…”

“…Complexes 7 − 9 exhibit a remarkable 1 J HgPt coupling of 28040−26750 Hz, suggesting strong Pt−Hg bonding. As far as we are aware, only two larger Pt−Hg coupling constants have been reported (34520, 37610 Hz), corresponding to dinuclear formally Pt +3 −Hg + complexes, while most data reported are in the range 11010−1602 Hz and do not correspond to formally Pt +3 −Hg + complexes. ,,,,− …”

“…25828 (11) > 23600 (5) > 15004 (12) > 10 (14945), which is very similar to that correlating the δ( 195 Pt) values. The 1 J PtHg for Pt(I)-Hg(I) complexes have been reported in the literature only for cationic species, and the values are lower (11010-4322 Hz) 10,12,31 than those in complexes 10-12. The smaller trans influence of bpy than that of PPh 3 in complexes 10 and 12 could be the reason for the greater value of its 1 J PtHg .…”

“…33 Most reported 1 J PtHg values are in the range 1600-11000 Hz, corresponding to complexes with weak Pt-Hg bonds or with coordination number at Pt e 5 or with formal oxidation state for Pt e +2. 12,15,27,30,31 Values as high as 34520 and 37610 Hz have been reported for octahedral complexes at Pt and linear at Hg with strong Pt +3 -Hg + bonds. 4 The values of 1 J PtHg in our complexes follow the order (in Hz) 9 (28040) > 8 (28026) > 7 (26750) .…”

“…The Pt−C(11) bond length [2.062(2) Å] is longer than those observed in complexes 7 [2.008(5)−2.024 (5) Å] and 9 [1.989(4) and 2.018(4) Å] in part due to the greater trans influence of PPh 3 than the O donor ligands and in part as a consequence of the lower formal oxidation state of the Pt atom in 10 (+1) than in 7 or 9 (+3) . The Pt−Hg distance [2.57586(19) Å] in 10 is shorter than those observed in 7 [2.6093(3) and 2.5914(3) Å] and 9 [2.5898(2) Å], all being in the range of Pt−Hg covalent bond lengths (2.666−2.513 Å). ,−

5 Ellipsoid representation of 10 (50% probability). Selected bond lengths (Å) and angles (deg): Pt−C(11) 2.062(2), Pt−P(2) 2.2923(6), Pt−P(1) 2.3248(6), Pt−Hg 2.57586(19), Hg−C(21) 2.152(2), O(11)−N(11) 1.226(2), O(12)−N(11) 1.230(2), O(16)−N(12) 1.215(3), O(17)−N(12) 1.220(3), O(21)−N(21) 1.224(3), O(22)−N(21) 1.227(3), O(26)−N(22) 1.225(3), O(27)−N(22) 1.218(3), N(11)−C(12) 1.470(3), N(12)−C(16) 1.484(3), N(21)−C(22) 1.477(3), N(22)−C(26) 1.473(3), C(11)−Pt−P(1) 91.72(6), P(2)−Pt−P(1) 103.70(2), C(11)−Pt−Hg 79.91(6), P(2)−Pt−Hg 85.220(16), C(21)−Hg−Pt 170.25(6), O(11)−N(11)−O(12) 123.0(2), O(11)−N(11)−C(12) 119.72(18), O(12)−N(11)−C(12) 117.23(19), O(16)−N(12)−O(17) 123.9(2), O(16)−N(12)−C(16) 118.0(2), O(17)−N(12)−C(16) 118.2(2), O(21)−N(21)−O(22) 124.4(2), O(21)−N(21)−C(22) 118.04(19), O(22)−N(21)−C(22) 117.6(2), O(27)−N(22)−O(26) 123.8(2), O(27)−N(22)−C(26) 118.1(2), O(26)−N(22)−C(26) 118.1(2).

…”

Bis(2,6-dinitroaryl)platinum Complexes. 2.1 Di- and Trinuclear Complexes Containing Pt−Hg Bonds

“…The two Pt−Hg bond distances are somewhat different in complex 7 [2.6093(3), 2.5914(3) Å], although Hg is trans to the same ligand, and are slightly longer than that in 9 [2.5898(2) Å]. These Pt−Hg distances lie in the range reported in other complexes containing covalent Pt−Hg bonds (2.666−2.513 Å), ,− but they are shorter than those in other complexes in which a metal−metal bond was described as Pt → Hg or could be thus formulated (2.835−2.650 Å) 4,5,14,15 or in higher nuclearity clusters (3.159−2.671 Å). , The Ar groups are bonded to platinum as chelating ligands and are mutually cis . The four Pt−C distances in 7 are not significantly different [range 2.024(5)−2.008(5) Å], but in 9 , they are slightly different [1.989(4), 2.018(4) Å].…”

“…Complexes 7 − 9 exhibit a remarkable 1 J HgPt coupling of 28040−26750 Hz, suggesting strong Pt−Hg bonding. As far as we are aware, only two larger Pt−Hg coupling constants have been reported (34520, 37610 Hz), corresponding to dinuclear formally Pt +3 −Hg + complexes, while most data reported are in the range 11010−1602 Hz and do not correspond to formally Pt +3 −Hg + complexes. ,,,,− …”

“…25828 (11) > 23600 (5) > 15004 (12) > 10 (14945), which is very similar to that correlating the δ( 195 Pt) values. The 1 J PtHg for Pt(I)-Hg(I) complexes have been reported in the literature only for cationic species, and the values are lower (11010-4322 Hz) 10,12,31 than those in complexes 10-12. The smaller trans influence of bpy than that of PPh 3 in complexes 10 and 12 could be the reason for the greater value of its 1 J PtHg .…”

“…33 Most reported 1 J PtHg values are in the range 1600-11000 Hz, corresponding to complexes with weak Pt-Hg bonds or with coordination number at Pt e 5 or with formal oxidation state for Pt e +2. 12,15,27,30,31 Values as high as 34520 and 37610 Hz have been reported for octahedral complexes at Pt and linear at Hg with strong Pt +3 -Hg + bonds. 4 The values of 1 J PtHg in our complexes follow the order (in Hz) 9 (28040) > 8 (28026) > 7 (26750) .…”

“…The Pt−C(11) bond length [2.062(2) Å] is longer than those observed in complexes 7 [2.008(5)−2.024 (5) Å] and 9 [1.989(4) and 2.018(4) Å] in part due to the greater trans influence of PPh 3 than the O donor ligands and in part as a consequence of the lower formal oxidation state of the Pt atom in 10 (+1) than in 7 or 9 (+3) . The Pt−Hg distance [2.57586(19) Å] in 10 is shorter than those observed in 7 [2.6093(3) and 2.5914(3) Å] and 9 [2.5898(2) Å], all being in the range of Pt−Hg covalent bond lengths (2.666−2.513 Å). ,−

5 Ellipsoid representation of 10 (50% probability). Selected bond lengths (Å) and angles (deg): Pt−C(11) 2.062(2), Pt−P(2) 2.2923(6), Pt−P(1) 2.3248(6), Pt−Hg 2.57586(19), Hg−C(21) 2.152(2), O(11)−N(11) 1.226(2), O(12)−N(11) 1.230(2), O(16)−N(12) 1.215(3), O(17)−N(12) 1.220(3), O(21)−N(21) 1.224(3), O(22)−N(21) 1.227(3), O(26)−N(22) 1.225(3), O(27)−N(22) 1.218(3), N(11)−C(12) 1.470(3), N(12)−C(16) 1.484(3), N(21)−C(22) 1.477(3), N(22)−C(26) 1.473(3), C(11)−Pt−P(1) 91.72(6), P(2)−Pt−P(1) 103.70(2), C(11)−Pt−Hg 79.91(6), P(2)−Pt−Hg 85.220(16), C(21)−Hg−Pt 170.25(6), O(11)−N(11)−O(12) 123.0(2), O(11)−N(11)−C(12) 119.72(18), O(12)−N(11)−C(12) 117.23(19), O(16)−N(12)−O(17) 123.9(2), O(16)−N(12)−C(16) 118.0(2), O(17)−N(12)−C(16) 118.2(2), O(21)−N(21)−O(22) 124.4(2), O(21)−N(21)−C(22) 118.04(19), O(22)−N(21)−C(22) 117.6(2), O(27)−N(22)−O(26) 123.8(2), O(27)−N(22)−C(26) 118.1(2), O(26)−N(22)−C(26) 118.1(2).

…”

Bis(2,6-dinitroaryl)platinum Complexes. 2.1 Di- and Trinuclear Complexes Containing Pt−Hg Bonds

“…The two Pt−Hg bond distances are somewhat different in complex 7 [2.6093(3), 2.5914(3) Å], although Hg is trans to the same ligand, and are slightly longer than that in 9 [2.5898(2) Å]. These Pt−Hg distances lie in the range reported in other complexes containing covalent Pt−Hg bonds (2.666−2.513 Å), ,− but they are shorter than those in other complexes in which a metal−metal bond was described as Pt → Hg or could be thus formulated (2.835−2.650 Å) 4,5,14,15 or in higher nuclearity clusters (3.159−2.671 Å). , The Ar groups are bonded to platinum as chelating ligands and are mutually cis . The four Pt−C distances in 7 are not significantly different [range 2.024(5)−2.008(5) Å], but in 9 , they are slightly different [1.989(4), 2.018(4) Å].…”

“…Complexes 7 − 9 exhibit a remarkable 1 J HgPt coupling of 28040−26750 Hz, suggesting strong Pt−Hg bonding. As far as we are aware, only two larger Pt−Hg coupling constants have been reported (34520, 37610 Hz), corresponding to dinuclear formally Pt +3 −Hg + complexes, while most data reported are in the range 11010−1602 Hz and do not correspond to formally Pt +3 −Hg + complexes. ,,,,− …”

“…25828 (11) > 23600 (5) > 15004 (12) > 10 (14945), which is very similar to that correlating the δ( 195 Pt) values. The 1 J PtHg for Pt(I)-Hg(I) complexes have been reported in the literature only for cationic species, and the values are lower (11010-4322 Hz) 10,12,31 than those in complexes 10-12. The smaller trans influence of bpy than that of PPh 3 in complexes 10 and 12 could be the reason for the greater value of its 1 J PtHg .…”

“…33 Most reported 1 J PtHg values are in the range 1600-11000 Hz, corresponding to complexes with weak Pt-Hg bonds or with coordination number at Pt e 5 or with formal oxidation state for Pt e +2. 12,15,27,30,31 Values as high as 34520 and 37610 Hz have been reported for octahedral complexes at Pt and linear at Hg with strong Pt +3 -Hg + bonds. 4 The values of 1 J PtHg in our complexes follow the order (in Hz) 9 (28040) > 8 (28026) > 7 (26750) .…”

“…The Pt−C(11) bond length [2.062(2) Å] is longer than those observed in complexes 7 [2.008(5)−2.024 (5) Å] and 9 [1.989(4) and 2.018(4) Å] in part due to the greater trans influence of PPh 3 than the O donor ligands and in part as a consequence of the lower formal oxidation state of the Pt atom in 10 (+1) than in 7 or 9 (+3) . The Pt−Hg distance [2.57586(19) Å] in 10 is shorter than those observed in 7 [2.6093(3) and 2.5914(3) Å] and 9 [2.5898(2) Å], all being in the range of Pt−Hg covalent bond lengths (2.666−2.513 Å). ,−

5 Ellipsoid representation of 10 (50% probability). Selected bond lengths (Å) and angles (deg): Pt−C(11) 2.062(2), Pt−P(2) 2.2923(6), Pt−P(1) 2.3248(6), Pt−Hg 2.57586(19), Hg−C(21) 2.152(2), O(11)−N(11) 1.226(2), O(12)−N(11) 1.230(2), O(16)−N(12) 1.215(3), O(17)−N(12) 1.220(3), O(21)−N(21) 1.224(3), O(22)−N(21) 1.227(3), O(26)−N(22) 1.225(3), O(27)−N(22) 1.218(3), N(11)−C(12) 1.470(3), N(12)−C(16) 1.484(3), N(21)−C(22) 1.477(3), N(22)−C(26) 1.473(3), C(11)−Pt−P(1) 91.72(6), P(2)−Pt−P(1) 103.70(2), C(11)−Pt−Hg 79.91(6), P(2)−Pt−Hg 85.220(16), C(21)−Hg−Pt 170.25(6), O(11)−N(11)−O(12) 123.0(2), O(11)−N(11)−C(12) 119.72(18), O(12)−N(11)−C(12) 117.23(19), O(16)−N(12)−O(17) 123.9(2), O(16)−N(12)−C(16) 118.0(2), O(17)−N(12)−C(16) 118.2(2), O(21)−N(21)−O(22) 124.4(2), O(21)−N(21)−C(22) 118.04(19), O(22)−N(21)−C(22) 117.6(2), O(27)−N(22)−O(26) 123.8(2), O(27)−N(22)−C(26) 118.1(2), O(26)−N(22)−C(26) 118.1(2).

…”

Bis(2,6-dinitroaryl)platinum Complexes. 2.1 Di- and Trinuclear Complexes Containing Pt−Hg Bonds

“…The two Pt−Hg bond distances are somewhat different in complex 7 [2.6093(3), 2.5914(3) Å], although Hg is trans to the same ligand, and are slightly longer than that in 9 [2.5898(2) Å]. These Pt−Hg distances lie in the range reported in other complexes containing covalent Pt−Hg bonds (2.666−2.513 Å), ,− but they are shorter than those in other complexes in which a metal−metal bond was described as Pt → Hg or could be thus formulated (2.835−2.650 Å) 4,5,14,15 or in higher nuclearity clusters (3.159−2.671 Å). , The Ar groups are bonded to platinum as chelating ligands and are mutually cis . The four Pt−C distances in 7 are not significantly different [range 2.024(5)−2.008(5) Å], but in 9 , they are slightly different [1.989(4), 2.018(4) Å].…”

“…Complexes 7 − 9 exhibit a remarkable 1 J HgPt coupling of 28040−26750 Hz, suggesting strong Pt−Hg bonding. As far as we are aware, only two larger Pt−Hg coupling constants have been reported (34520, 37610 Hz), corresponding to dinuclear formally Pt +3 −Hg + complexes, while most data reported are in the range 11010−1602 Hz and do not correspond to formally Pt +3 −Hg + complexes. ,,,,− …”

“…25828 (11) > 23600 (5) > 15004 (12) > 10 (14945), which is very similar to that correlating the δ( 195 Pt) values. The 1 J PtHg for Pt(I)-Hg(I) complexes have been reported in the literature only for cationic species, and the values are lower (11010-4322 Hz) 10,12,31 than those in complexes 10-12. The smaller trans influence of bpy than that of PPh 3 in complexes 10 and 12 could be the reason for the greater value of its 1 J PtHg .…”

“…33 Most reported 1 J PtHg values are in the range 1600-11000 Hz, corresponding to complexes with weak Pt-Hg bonds or with coordination number at Pt e 5 or with formal oxidation state for Pt e +2. 12,15,27,30,31 Values as high as 34520 and 37610 Hz have been reported for octahedral complexes at Pt and linear at Hg with strong Pt +3 -Hg + bonds. 4 The values of 1 J PtHg in our complexes follow the order (in Hz) 9 (28040) > 8 (28026) > 7 (26750) .…”

“…The Pt−C(11) bond length [2.062(2) Å] is longer than those observed in complexes 7 [2.008(5)−2.024 (5) Å] and 9 [1.989(4) and 2.018(4) Å] in part due to the greater trans influence of PPh 3 than the O donor ligands and in part as a consequence of the lower formal oxidation state of the Pt atom in 10 (+1) than in 7 or 9 (+3) . The Pt−Hg distance [2.57586(19) Å] in 10 is shorter than those observed in 7 [2.6093(3) and 2.5914(3) Å] and 9 [2.5898(2) Å], all being in the range of Pt−Hg covalent bond lengths (2.666−2.513 Å). ,−

5 Ellipsoid representation of 10 (50% probability). Selected bond lengths (Å) and angles (deg): Pt−C(11) 2.062(2), Pt−P(2) 2.2923(6), Pt−P(1) 2.3248(6), Pt−Hg 2.57586(19), Hg−C(21) 2.152(2), O(11)−N(11) 1.226(2), O(12)−N(11) 1.230(2), O(16)−N(12) 1.215(3), O(17)−N(12) 1.220(3), O(21)−N(21) 1.224(3), O(22)−N(21) 1.227(3), O(26)−N(22) 1.225(3), O(27)−N(22) 1.218(3), N(11)−C(12) 1.470(3), N(12)−C(16) 1.484(3), N(21)−C(22) 1.477(3), N(22)−C(26) 1.473(3), C(11)−Pt−P(1) 91.72(6), P(2)−Pt−P(1) 103.70(2), C(11)−Pt−Hg 79.91(6), P(2)−Pt−Hg 85.220(16), C(21)−Hg−Pt 170.25(6), O(11)−N(11)−O(12) 123.0(2), O(11)−N(11)−C(12) 119.72(18), O(12)−N(11)−C(12) 117.23(19), O(16)−N(12)−O(17) 123.9(2), O(16)−N(12)−C(16) 118.0(2), O(17)−N(12)−C(16) 118.2(2), O(21)−N(21)−O(22) 124.4(2), O(21)−N(21)−C(22) 118.04(19), O(22)−N(21)−C(22) 117.6(2), O(27)−N(22)−O(26) 123.8(2), O(27)−N(22)−C(26) 118.1(2), O(26)−N(22)−C(26) 118.1(2).

…”