Recent Advances in the Chemistry of Metal Carbamates Giulio Bresciani, Lorenzo Biancalana, Guido Pampaloni and Fabio Marchetti Dipartimento di Chimica e Chimica Industriale, Università di Pisa, Via G. Moruzzi 13, I-56124 Pisa, Italy SUPPORTING INFORMATION Table of contents Page(s) Table S1. Rate and equilibrium constants for carbamato formation and hydrolysis in S2-S3 water. Table S2. Selected X-ray bond distances (Å) and angles (°) in amidinium/guanidinium S4 CO 2 adducts. Table S3. Selected bond distances (Å) and angles (°) for carbamato ligands in metal S5-S9 complexes. Table S4. NMR and IR data related to the NCO 2 moiety in metal carbamato complexes. S10-S13 References S14-S23 S1 Table S1. Rate (k) and equilibrium (K CBM ) constants for the carbamato formation and equilibrium constant (KHYD ) for the carbamato hydrolysis at 18 °C in water. Amine pK b[a] k (M-1 min -1) KCBM KHYD Ref. NH 3 4.76 3.8 × 10 3 2.3 × 10 3 4.4 × 10 -1 [1] Primary amines NH 2Me 3.38 8.3 × 10 4 4.0 × 10 6 6.0 × 10 -3 [1] NH 2Et 3.19 1.5 × 10 5 2.0 × 10 6 1.8 × 10 -2 [1] NH 2Pr 3.41 1.6 × 10 5 1.5 × 10 6 1.3 × 10 -2 [1] NH 2iPr 3.37 6.8 × 10 4 3.6 × 10 5 6.3 × 10 -2 [1] NH 2Bn 4.74 1.1 × 10 5 8.5 × 10 4 1.2 × 10 -2 [1] NH 2Ph 9.30 ≈10 3 8.1 × 10 -3 3.6 [1] NH 2allyl 4.38 1.1 × 10 5 1.6 × 10 5 1.5 × 10 -2 [1] NH 2Bu 3.24 2.0 × 10 5 1.1 × 10 5 1.6 × 10 -2 [1] NH 2sBu 3.44 7.1 × 10 4 3.8 × 10 5 4.9 × 10 -2 [1] NH 2iBu 3.58 1.6 × 10 5 1.3 × 10 6 1.0 × 10 -2 [1] NH 2tBu 3.55 1.9 × 10 4 1.1 × 10 5 1.0 × 10 -1 [1] Secondary amines NHMe 2 3.22 6.7 × 10 5 1.6 × 10 6 2.2 × 10 -2 [1] NHEt 2 3.51 2.9 × 10 5 7.4 × 10 4 2.4 × 10 -1 [1] NHPr 2 3.09 3.0 × 10 5 3.0 × 10 5 1.5 × 10 -1 [1] NH iPr 2 3.17 − None − [1] NHBu 2 2.54 3.1 × 10 5 4.6 × 10 5 1.9 × 10 -1 [1] NH sBu 2 − − None − [1] NH iBu 2 3.41 1.3 × 10 5 1.9 × 10 5 1.2 × 10 -1 [1] Piperidine 2.95 7.8 × 10 5 7.9 × 10 5 8.1 × 10 -2 [1] 3-MPD 3.12 − 6.9 × 10 6 6.2 × 10 -3 [2] 4-MPD 3.06 − 5.9 × 10 6 8.3 × 10 -3 [2] Pyrrolidine 3.16 3.5 × 10 6 1.9 × 10 7 2.0 × 10 -3 [3,4] Substituted amines MEA 4.42 8.3 × 10 4 6.0 × 10 4 1.9 × 10 -2 [1] DEA 4.98 1.0 × 10 5 2.1 × 10 3 1.5 × 10 -1 [1] 1-AP [b] 4.75 3.2 × 10 5 9.6 × 10 3 1.1 × 10 -1 [3] 2-AP [b] 4.75 6.0 × 10 4 4.0 × 10 3 2.5 × 10 -1 [5] MPA [b] 4.18 5.4 × 10 5 2.5 × 10 5 1.5 × 10 -2 [5] S2 AMP [b] 4.73 − None − [5] 4-PIPDM [b] 3.71 1.3 × 10 6 2.7 × 10 5 4.1 × 10 -2 [3,4] 4-PIPDE [b] 3.65 − 3.0 × 10 5 4.2 × 10 -2 [4] Morpholine [b] 5.78 1.6 × 10 5 1.4 × 10 3 6.8 × 10 -2 [3,4] Thiomorpholine [b] 5.57 1.9 × 10 5 9.3 × 10 2 1.6 × 10 -1 [3,4] 4.50 − 5.5 × 10 4 3.2 × 10 -2 Piperazine [6] 8.67 − 2.6 × 10 -1 4.6 × 10 -1 MPIPZ 4.96 − 5.1 × 10 3 1.2 × 10 -1 [3] 4-AMTHP [b] 4.37 3.6 × 10 5 1.9 × 10 5 1.3 × 10 -2 [7] Taurine [b],[c] 5.19 − 7.1 × 10 3 5.1 × 10 -2 [8] Amino acids Glycine [d] 4.49 3.2 × 10 5 4.4 × 10 4 4.2 × 10 -2 [9] Sarcosine [b],[d] 4.22 1.1 × 10 6 3.3 × 10 4 1.0 × 10 -1 [10] a-Alanine [d] 4.40 6.6 × 10 4 1.8 × 10 4 1.1 × 10 -1 [11] b-Alanine [d] 3.86 1.1 × 10 5 1.9 × 10 5 3.1 × 10 -2 [11] Proline [c] 3.57 − 5.4 × 10 5 2.8 × 10 -2 [12] 4.44 [e] − 1.7 × 10 4 1.2 × 10 -1 Lysine [b],[c] [13] 3.24 [f] − 6.3 × 10 4 5.1 × 10 -1 [a] pK b values are from ref. [1–9,12,13]. For a list of pKb see ref. [14,15]. (K w = 10 -14.27 ); [b] Measured at 25°C; [c] Potassium salt; [d] Sodium Salt; [e] Deprotonation of the a-amino group; [f] Deprotonation of the amino group on the lateral chain; 3-MPD = 3-methylpiperidine, 4-MPD = 4-methylpiperidine, MEA = monoethanolamine, DEA = diethanolamine, 1-AP = 2-amino-1-propanol, 2-AP = 1-amino-2-propanol, MPA = 3-amino-1-propanol, AMP = 2-amino-2-methyl-1-propanol, 4-PIPDM = 4-piperidinemethanol, 4-PIPDE = 4-piperidineethanol, MPIPZ = 1-methylpiperazine, 4-AMTHP = 4-aminomethyltetrahydropyran S3 Table S2. Selected X-ray bond distances (Å) and angles (°) in amidinium/guanidinium CO 2 adducts. N1-C1 C1-O1 C1-O2 N1-C2 C2-N2 C2-N3 O1-C1-O2 C1-N1-C2-N2 Compound Ref. (Å) (Å) (Å) (Å) (Å) (Å) (((α(ααα)) (°) (βββ)β))) ( °))) 1.480(3) 1.257(3) 1.229(2) 1.369(3) 1.332(2) 1.338(3) 128.6(2) 4.4(2) [16] 1.513(3) 1.233(3) 1.228(3) 1.330(3) 1.322(3) - 132.2(2) 9.1(2) [17] 1.439(2) 1.248(1) 1.243(1) 1.373(1) 1.355(1) 1.349(2) 130.6(1) 88.9(2) [17] 1.432(1) 1.251(1) 1.243(1) 1.368(1) 1.338(1) 1.392(1) 129.09(9) 68.9(1) [17] S4 Table S3. Selected bond distances (Å) and angles (°) for carbamato ligands in metal complexes (2004-2020). Metal center Carbamate coordination C-O1 (Å) C-O2 (Å) C-N (Å) O-C-O (°) Ref. Al(III) B/2 1.284(2) 1.282(2) 1.347(2) 120.0(1) [18] Al(III) B/2 1.300(5) 1.282(5) 1.326(5) 122.3(4) [19] Al(III) B/2 1.280(4) 1.280(4) 1.335(4) 120.4(3) [20] Bi(III) M/1 1.295(5) 1.250(6) 1.348(4) 123.9(4) [21] B/2 1.288(4) 1.265(4) 1.360(4) 122.9(3) Bi(III) C/2 1.295(4) 1.274(4) 1.342(4) 120.5(3) [22] C/1 1.299(4) 1.260(4) 1.355(4) 119.9(3) C/1 1.28(1) 1.26(2) 1.35(2) 120(1) B/2 1.28(1) 1.26(1) 1.34(1) 121(1) Ce(III) C/2 1.28(1) 1.28(1) 1.35(1) 119(1) [23] B/3 1.34(1) 1.25(1) 1.33(1) 120.6(9) B/4 1.311(9) 1.28(1) 1.34(1) 119.7(8) M/1 1.26(1) 1.21(1) 1.44(1) 128.4(8) Ce(III) C/2 1.284(9) 1.23(1) 1.39(1) 123.5(7) B/3 1.26(1) 1.23(1) 1.44(1) 128.7(8) [24] Ce(III) M/1 1.29(3) 1.20(3) 1.42(2) 129.0(2) Ce(IV) M/1 1.293(2) 1.201(3) 1.438(3) 128.3(2) Ce(IV) B/2 1.253(4) 1.243(4) 1.421(4) 128.1(2) C/1 1.269(8) 1.254(7) 1.357(5) 118.3(5) Ce(IV) B/2 1.277(4) 1.271(5) 1.362(6) 123.8(4) [23] C/2 1.279(7) 1.270(4) 1.346(7) 119.6(4) Cu(II) M/1 1.30(3) 1.20(3) 1.39(3) 131(2) [25] Cu(II) C/2 1.35(2) 1.25(2) 1.31(2) 118(1) [26] Cu(II) B/2 1.269(6) 1.259(6) 1.375(6) 126.7(4) [27] Cu(II) C/2 1.289(4) 1.238(4) 1.375(4) 123.6(3) M/1 1.281(3) 1.236(3) 1.375(3) 125.9(2) [28] Cu(II) B/2 1.280(3) 1.280(3) 1.367(3) 125.2(2) S5 C/1 1.28(1) 1.28(1) 1.34(1) 119.0(7) Dy(III) B/2 1.275(8) 1.27(1) 1.36(1) 122.7(7) [29] B/3 1.293(9) 1.25(1) 1.372(8) 121.3(6) Dy(III) M/1 1.272(6) 1.235(7) 1.373(8) 125.0(5) [30] C/1 1.295(8) 1.260(9) 1.369(9) 120.5(6) Er(III) B/2 1.272(7) 1.263(6) 1.346(8) 123.3(5) [31] B/3 1.305(6) 1.266(7) 1.348(6) 121.0(4) Er(III) D/2 1.333(6) 1.277(6) 1.315(6) 115.6(4) [32] C/1 1.27(1) 1.26(1) 1.37(1) 120.6(8) Eu(III) B/2 1.278(8) 1.254(6) 1.336(7) 123.1(5) [31] B/3 1.300(7) 1.253(6) 1.340(8) 122.2(5) Fe(III) B/2 1.280(5) 1.269(5) 1.346(6) 125.3(4) [33] Fe(II) M/1 1.293(3) 1.204(3) 1.401(4) 128.4(2) [34] Ga(III) B/2 1.283(4) 1.281(5) 1.345(5) 122.2(3) [35] C/1 1.33(1) 1.252(8) 1.39(1) 117.1(7) Ga(III) B/2 1.30(1) 1.30(1) 1.37(1) 122.3(7) [36] Ga(III) B/2 1.283(3) 1.276(3) 1.354(3) 121.0(2) Ga(III) C/1 1.293(3) 1.290(3) 1.351(3) 114.7(2) C/1 1.32(2) 1.24(2) 1.36(2) 117(1) Hf(IV) [37] B/2 1.29(1) 1.26(2) 1.31(2) 121(1) Ir(I) M/1 1.300(9) 1.23(1) 1.36(1) 125.5(8) [38] Ir(III) M/1 1.254(5) 1.231(7) 1.391(7) 124.0(5) Ir(III) M/1 1.252(7) 1.251(6) 1.401(8) 124.8(5) [39] Ir(III) M/1 1.26(1) 1.22(1) 1.395(8) 124.2(7) Ir(III) M/1 1.275(3) 1.219(2) 1.474(3) 128.7(2) [40] Ir(III) C/1 1.290(5) 1.275(5) 1.334(6) 117.7(4) [41] Ir(III) D/1 1.366(4) 1.237(4) 1.327(4) 120.7 C/1 1.25(1) 1.25(1) 1.39(1) 122.0(9) La(III) C/2 1.29(1) 1.262(9) 1.360(9) 120.5(7) [42] C/3 1.28(1) 1.27(1) 1.35(1) 120.1(8) Li(I) B/2 1.261(2) 1.255(2) 1.401(2) 124.3((1)) B/2 1.262(4) 1.254(4) 1.391(5) 122.21(3) [18] Li(I) B/3 1.285(3) 1.245(5) 1.379(4) 121.53(3) B/4 1.273(3) 1.273(4) 1.361(5) 121.0(3) B/2 1.264(4) 1.262(4) 1.338(5) 123.1(3) Li(I) B/3 1.264(2) 1.261(3) 1.355(4) 120.9(2) [43] B/5 1.279(3) 1.272(3) 1.342(3) 120.3(2) S6 C/5 1.261(3) 1.251(4) 1.333(3) 121.2(3) Li(I) B/3 1.262(3) 1.234(3) 1.424(4) 127.8(3) C/1 1.30(1) 1.26(2) 1.33(2) 119(1) Lu(III) B/2 1.26(1) 1.25(1) 1.36(1) 124.0(9) [31] B/3 1.309(9) 1.24(1) 1.34(1) 121.6(8) Mg(II) B/2 1.267(3) 1.266(3) 1.368(3) 124.9(2) B/2 1.262(5) 1.259(5) 1.391(5) 126.5(3) [44] Mg(II) C/3 1.276(4) 1.272(4) 1.353(5) 119.8(3) B/2 1.28(2) 1.24(2) 1.41(2) 124.5(2) C/2 1.30(2) 1.22(2) 1.368 124.0(1) Mg(II) [45] B/3 1.28(2) 1.28(2) 1.32(2) 122.0(1) M/2 1.28(2) 1.28(2) 1.35(2) 124.3(1) B/2 1.261(9) 1.25(1) 1.348(9) 123.7(6) Mn(II)/Mn(III) [46] B/3 1.267(5) 1.258(4) 1.333(4) 122.6(3) C/1 1.306(6) 1.295(8) 1.323(9) 115.3(5) Nb(V) [47] B/2 1.304(7) 1.278(8) 1.33(1) 120.8(6) Nd(III) C/2 1.307(5) 1.250(6) 1.347(6) 119.1(4) [48] Ni(II) B/2 1.264(3) 1.255(3) 1.368(3) 129.0(2) [49] Ni(II) B/2 1.27(2) 1.22(2) 1.44(2) 130(1) Ni(II) M/1 1.263(8) 1.24(1) 1.37(1) 127.3(6) [50] Ni(II) M/1 1.286(4) 1.254(3) 1.361(4) 124.6(3) [51] Ni(II) D/1 1.340(2) 1.229(2) 1.360(2) 123.7(2) [52] Ni(II) B/2 1.325(7) 1.322(8) 1.291(8) 118.6(5) [53] Ni(II) M/1 1.288(2) 1.243(2) 1.372(2) 124.7(1) [54] Ni(II) M/1 1.280(3) 1.211(4) 1.388(4) 126.5(3) [55] Ni(II) M/1 1.288(2) 1.233(2) 1.387(2) 126.5(1) [56] Ni(II) C/1 1.284(4) 1.239(4) 1.385(4) 124.2(3) Pd(II) D/1 1.316(2) 1.219(2) 1.401(3) 124.2(2) [57] Pd(II) M/1 1.299(4) 1.230(5) 1.382(5) 125.0(3) [58] Pt(IV) M/1 1.326(4) 1.235(4) 1.354(4) 125.1(3) Pt(IV) M/1 1.323(3) 1.240(2) 1.346(3) 125.4(2) [59] Pt(IV) M/1 1.335(4) 1.233(4) 1.344(4) 125.0(3) Pt(IV) M/1 1.325(5) 1.219(5) 1.354(6) 126.1(4) Pt(IV) M/1 1.321(3) 1.236(3) 1.340(3) 125.8(2) [60] Pt(IV) M/1 1.310(4) 1.242(5) 1.346(5) 124.6(4) [61] Pt(IV) M/1 1.327(4) 1.249(5) 1.336(6) 125.0(3) Re(I) M/1 1.27(1) 1.25(1) 1.40(1) 125.1(7) [62] S7 Rh(III) C/1 1.281(4) 1.263(4) 1.352(4) 119.6(3) [63] Ru(II) C/1 1.28(3) 1.24(3) 1.39(4) 123(3) [64] Ru(II) M/1 1.301(5) 1.229(5) 1.457(6) 127.3(4) [65] Ru(II) M/1 1.281(2) 1.243(2) 1.390(2) 126.5(1) [66] Sc(III) M/1-c 1.318(5) 1.209(5) 1.425(5) 124.3(4) [67] C/1 1.289(6) 1.255(7) 1.364(9) 120.4(5) Sm(III) B/2 1.273(4) 1.270(6) 1.358(6) 123.4(4) [23] B/3 1.304(4) 1.262(4) 1.345(6) 121.6(3) Sn(II) M/1 1.304(3) 1.238(3) 1.366(2) 121.7(2) [68] C/1 1.280(3) 1.272(3)